CN1282540C

CN1282540C - Process for producing photochromic layered product

Info

Publication number: CN1282540C
Application number: CNB038014025A
Authority: CN
Inventors: 森力宏; 名乡洋信; 百田润二; 和泉忍
Original assignee: Tokuyama Corp
Current assignee: Tokuyama Corp
Priority date: 2002-05-27
Filing date: 2003-05-26
Publication date: 2006-11-01
Anticipated expiration: 2023-05-26
Also published as: ES2326875T3; JP4225970B2; US8409670B2; AU2003234848C1; US20070065633A1; KR100812870B1; AU2003234848A1; AU2003234848B2; CN1578727A; EP1561571B1; EP1561571A4; WO2003099550A1; DE60327545D1; KR20040111328A; EP1561571A1; JPWO2003099550A1

Abstract

A process for producing a photochromic layered product, characterized by preparing a base having a curved surface, applying a photopolymerizable/curable composition containing a photochromic compound and a phosphorus compound photopolymerization initiator to the curved surface of the base, and curing the photopolymerizable/curable composition by irradiation with actinic energy rays having a distribution in which the relative intensity of components ranging in wavelength from 200 nm to 300 nm, excluding 300 nm, accounts for 0 to 5%, the relative intensity of components ranging in wavelength from 300 nm to 400 nm, excluding 400 nm, accounts for 25 to 75%, and the relative intensity of components ranging in wavelength from 400 nm to 500 nm accounts for 25 to 75%, while keeping the base at 100 DEG C or lower. Thus, a homogeneous coating film having an even small thickness and containing a photochromic compound in a high concentration can be formed.

Description

The method for preparing photochromic laminate product

Technical field

The present invention relates to a kind of method with the polymer film prepared layer compressing tablet that shows photochromic property.More particularly, the present invention relates to the method for a kind of preparation, relate to photopolymerization and cured compositions (being preferably used as the coating that forms polymer film among the above-mentioned preparation method) and relate to the laminate that is preferably used as by the optical goods of above-mentioned preparation method's preparation as the laminate of optical goods (as photochromic glasses) with photochromic property.

Background document

Photochromic is when containing ultraviolet light such as sunlight or mercury lamp light radiation, compound can change color fast, and ought be no longer with light radiation and be placed on dark local time, this compound reverts to the reversible action of its priming color, photochromic existing various application.

For example, also can be with the photochromic eyewear art that is used for, the polymerisable monomer that has added the various photochromic compounds with above-mentioned performance by curing obtains having the plastic lens of photochromic property.The photochromic compound that can be advantageously used in these application has fulgimide compound, spiral shell piperazine compound and chromene compounds.

In order to prepare plastic lens, following method has been proposed with photochromic property:

1. with the method (infusion method) of photochromic compound with lens (not having photochromic property) surface infiltration;

2. by photochromic compound is dissolved in the monomer, polymerization then directly obtains the method (substance law) of photochromic lens

3. form at lens surface and have the method (rubbing method) of photochromic property thin layer.

Yet, for by above-mentioned infusion method 1. or substance law 2. obtain favourable photochromic property, the substrate of lens must be designed to help showing photochromic property, and restricted to spendable substrates of lenses.For example, reduce the glass transformation temperature (Tg) of substrates of lenses based on following design principle:, perhaps make the molecule of photochromic compound be easy to activity the expansion of the free space between the polymer even the molecule of photochromic compound also is easy to move in polymer.

As for the example of the monomer that forms substrates of lenses, U.S. Patent number 5739243 proposes to use special long-chain aklylene glycol dimethylacrylate and the multifunctional methacrylate with three or more radical polymerization group.This method makes the photochromic lens that obtains having more excellent colour density and fading rate become possibility.Yet,, need to reduce the glass transformation temperature Tg of substrate to improve photochromic property and to improve the performance of using photochromic compound swelling substrate according to this method.As a result, the substrate too soft following new problem that produced that becomes: the hardness of substrate reduces, heat resistance reduces and optical strain becomes big.Can address the above problem (for example, seeing that pct international patent discloses 01/05854) by being designed for the monomer and the photochromic material that obtain the plastic lens substrate.Yet 1. or 2.,, can not avoid that described substrate is had some restrictions although used said method.

On the contrary, according to above-mentioned rubbing method 3., can give various substrates of lenses with photochromic property and be not subjected to any restriction.But, when using rubbing method, also fail to develop and form that to have one deck thin and uniformly, the substrate performance is had no side effect, has sufficiently high case hardness and has the technology of filming of excellent photochromic property.

For example, WO98/37115 propose to use photochromic compound is dissolved in the urethane oligomer and the coating solution that obtains coating lens surface, the method for Gu Huaing subsequently.But, the resin that is obtained by the curing urethane oligomer has the low degree of cross linking, cause photochromic property to vary with temperature bigger difference, in addition, also comprise following defective: when being applied to hard coating on the photochromic coating, photochromic compound can be entered in the solution of hard coating by wash-out.

U.S. Patent number 5914174 has proposed a kind of preparation has the photochromic lens of photochromic polymer film on the convex surface of ordinary lens method, described method comprises in polymerisable compound simple function, dual functional and polyfunctional free yl polymerizating monomer by photochromic compound is dissolved in, allow described polymerisable compound flow in the gap of fixing by elastic body shim or partition between plastic lens and the glass mold, and the polymerization polymerisable compound, thereby on the convex surface of lens, obtain photochromic film.Yet the thickness of the photochromic polymer film (coating) that obtains according to this method is 200 to 500 μ m, and the polymer thin film strength brings bad influence for described plastic lens.The intensity that promptly is the strength ratio of the photochromic lens ordinary lens that do not have the coated polymeric film is low.In addition,, be difficult in and keep little and consistent gap between plastic lens and the glass mold, be difficult to form and have thin and the thin polymer film of homogeneous thickness according to this method.When described lens surface had complicated shape, it is obvious especially that this trend becomes.

In addition, WO01/02449 also provides a kind of preparation to have the method for photochromic lens that thickness is the photochromic polymer film of about 20 μ m on the convex surface of ordinary lens, described method is dissolved in the polymerisable compound that contains two or more difunctionals (methyl) acrylate by the photochromic compound with 5 to 10 weight portions, described polymerisable compound is coated on the convex surface of lens by spin coating, in being replaced into nitrogen atmosphere with the lens light polymerization, thereby on the convex surface of lens, form the photochromic polymer film.According to this method, lens surface has been coated with the photochromic films that can show very dense color, keeps thickness (about 20 μ m) can the performance of substrate not to be had side effects simultaneously.But above-mentioned disclosing both do not considered the uniformity of thickness or the uniformity of filming, and do not consider the optical property of the lens of gained yet.

Usually, Photoepolymerizationinitiater initiater and photochromic compound are all available ultraviolet ray excited.When the illumination that all can exist with both, Photoepolymerizationinitiater initiater decomposes hardly, so polymerization is difficult to take place.Contain the polymerizable and the cured compositions of photochromic compound and Photoepolymerizationinitiater initiater by use, the inventor has studied the influence of membrance casting condition to filming.As a result, found the following problem relevant with rubbing method.

(i) after the time lengthening of polymerization cost, substrate surface (having formed film on it) has been lost planarization.When lens surface had curved surface as glasses, coating reagent let droop to drip and makes and be difficult to obtain the uniform film of thickness.

(ii) when prolong the ultraviolet time of continuous radiation under the not enough condition of extent of polymerization, described radical reaction is interrupted, although because air by nitrogen replacement, still containing minute quantity oxygen in the air influences this reaction.Specifically, non-polymeric layer, the film that can not obtain having sufficiently high case hardness have been formed in part near the surface.

(iii) under the not enough condition of extent of polymerization, prolong the time of ultraviolet radiation, can cause photochromic compound to lose efficacy because of photooxidation.

(iv) carry out radiation to shorten the light radiation time, promote polymerization simultaneously with the activation-energy-ray that contains intensive ultraviolet, when solidifying because light source and ultrared influence, lens surface be subjected to the high temperature heating (for example 120 ℃ or higher or 200 ℃ or higher).When using the low plastic lens substrate of hear resistance, described lens itself are understood thermal deformation.

(v) because coating surface is different with inner rate of polymerization, different the making of shrinkage factor is difficult to obtain the homogeneous polymer film.

Of the present invention open

As mentioned above, described rubbing method is the excellent process of giving any substrate photochromic property, have thin on the substrate curved surface and thereby homogeneous thickness makes the performance (specifically referring to mechanical performance and optical property) of substrate be without prejudice but still can not be formed on, all even have filming of high surface hardness and excellent photochromic property.

Therefore, the purpose of this invention is to provide and to form above-mentioned technology of filming.

In order to address the above problem, the inventor has carried out deep research, find following true: the photopolymerization and the hardening composition that will contain the high concentration photochromic compound are applied on the substrate with curved surface, and carry out radiation curing with activation-energy-ray with special relative intensity distribution (relative intensity of wavelength component distributes), keep the temperature of described substrate to be no more than specified temp simultaneously, can obtain the irrealizable high evenness photochromic coating of prior art like this, thereby finish the present invention.

Just, the invention provides the method for prepared layer compressing tablet, described method comprises:

The substrate of preparation band curved surface;

To contain on the photopolymerization of photochromic compound and phosphorous Photoepolymerizationinitiater initiater and the curved surface that cured compositions is coated onto described substrate; And

Described photopolymerization of activation-energy-ray radiation curing and cured compositions that apparatus has following relative intensity to distribute: be not shorter than 400nm but be 25 to 75% no longer than the relative intensity of the wavelength component of 500nm, but the relative intensity that is not shorter than 300nm is shorter than the wavelength component of 400nm is 25 to 75%, but the relative intensity that is not shorter than 200nm is shorter than the wavelength component of 300nm is 0 to 5%, keeps the temperature of described substrate not to be higher than 100 ℃ simultaneously.

According to the preparation method of the invention described above, (just, in open system) solidifies photopolymerization and cured compositions under gas atmosphere, and do not need to use mould to improve productive rate.When using mould, described mould is necessary for the mould of particular design, and is difficult to accurately form the film of (being specially 1 to the 50 μ m) thickness that has 1 to 100 μ m.

In the present invention, also will contain the photopolymerization of photochromic compound and hardening composition and as the phosphorous Photoepolymerizationinitiater initiater blend of Photoepolymerizationinitiater initiater.By implementing to solidify with described activation-energy-ray (making its relative intensity have above-mentioned distribution) radiation by adjusting, described curing is finished at short notice, can effectively avoid being included in a large amount of photochromic compounds in the described curable compositions by photo damage, and on the substrate curved surface, be formed uniformly polymer film.Phosphorous Photoepolymerizationinitiater initiater generally not only works with ultraviolet ray, but also quilt excites division to cause described Raolical polymerizable at the activation-energy-ray that wavelength is not shorter than the visible region of 400nm.Even when photopolymerization and hardening composition are mixed with the photochromic compound of high concentration, the relative intensity that also can regulate activation-energy-ray as mentioned above distributes, the relative intensity of its ultraviolet range is reduced (described photochromic compound is by the rays excite of ultra-violet (UV) band), therefore, cause the influence that described Raolical polymerizable just is not subjected to described photochromic compound with such activation-energy-ray radiation.Therefore, can promptly allow the coating inside of photopolymerization and cured compositions realize polymerization and curing, avoid described photochromic compound by photo damage effectively simultaneously.After division, because himself photobleaching effect, described phosphorous polymerization initiator can not further absorb visible light, even therefore also can the continuous trigger initiation reaction in coating depth direction, also can solidify equably even reach coating inside so deeply.

Here, the gross area of the activation-energy-ray intensity between 200 to 500nm is used as 100%, the relative intensity of activation-energy-ray is represented the ratio of the area of the activation-energy-ray intensity in certain wave-length coverage.Make the colour filter (for example hard soda-lime glass) that contains ultraviolet activation-energy-ray and reduce to regulate the distribution of activation-energy-ray relative intensity at an easy rate by the component that makes wavelength be shorter than 300nm.

Preparation method according to the invention described above, effectively avoided photochromic compound by photo damage, and solidify through inner quickly and evenly, make that effectively avoid being coated on on-chip curable compositions hangs down and drip down, it is uniform and contain the photochromic polymer film of high concentration photochromic compound therefore can to form thickness on substrate surface.

According to the present invention, except that described phosphorous Photoepolymerizationinitiater initiater, also need to use together other Photoepolymerizationinitiater initiater.Therefore, above-mentioned phosphorous Photoepolymerizationinitiater initiater usable as internal solidifies Photoepolymerizationinitiater initiater, and other Photoepolymerizationinitiater initiater can trigger initiation reaction with ultraviolet ray simultaneously.Therefore, at the near surface of curable compositions coating, other Photoepolymerizationinitiater initiater is influenced by oxygen hardly, can be used as the surface cure polymerization initiator.Like this,, use phosphorous Photoepolymerizationinitiater initiater and other Photoepolymerizationinitiater initiater, can form the photochromic polymer film that one deck is all evenly solidified to inside by the surface even in the atmosphere that contains trace oxygen (tens to a hundreds of ppm), be cured.In other words, can enlarge the allowed band of oxygen concentration in the atmosphere that realizes polymerization and curing.Therefore, adjustable solar term atmosphere (as being replaced into nitrogen) is gentle condition, described polymerization can be finished at short notice with curing, and can effectively prevent to be applied to on-chip curable compositions and hang down and to drip down, this is for the thickness generation deviation that prevents the photochromic polymer film and wrinkle to occur be very favorable.In addition, polymer film demonstrates the case hardness of enhancing, is favourable for improving mutual bonding between polymer film and substrate or the hard coating.

When not using phosphorous Photoepolymerizationinitiater initiater when only using other Photoepolymerizationinitiater initiater, does not almost solidify the inside of coating, still still contains the curable compositions of high concentration photochromic compound.In order to allow coating solidify, must use other Photoepolymerizationinitiater initiater in a large number until inside.The result lost efficacy described photochromic compound.

Also keep the temperature of substrate not to be higher than 100 ℃ when in the present invention, implementing to solidify.Therefore, form thickness and kept uniform photochromic polymer film, effectively avoided described substrate thermal deformation.Even use the thin substrate (for example thin lens) that is not more than 2mm as the thickness at curvature of curved surface center, also can form indeformable photochromic polymer film.For the temperature that keeps substrate is not higher than 100 ℃, need after distributing, the relative intensity of regulating activation-energy-ray allow it pass through the heat ray edge filter.

In the present invention, photopolymerization and the hardening composition that is used to prepare photochromic laminate comprises (A) free yl polymerizating monomer, (B) photochromic compound and (C) Photoepolymerizationinitiater initiater component, the content of described photochromic compound (B) is 0.2 to 20% weight, in per 100 weight portion free yl polymerizating monomers (A), phosphorous Photoepolymerizationinitiater initiater accounts for 0.01 to 10 weight portion and other Photoepolymerizationinitiater initiater except that phosphorous Photoepolymerizationinitiater initiater accounts for 0.01 to 10 weight portion in the Photoepolymerizationinitiater initiater component (C) that is comprised.

Preparation method according to the invention described above, can obtain to have the laminate of the substrate of curved surface, forming thickness on the curved surface of described substrate is the polymer film of 1 to 100 μ m, described polymer film comprises the photochromic compound of 0.2 to 20% weight, wherein lamination the substrate curved surface before the polymer film refraction at spherical surface ability (hereinafter referred is the refraction at spherical surface rate of substrate) and formed difference between the refraction at spherical surface ability (hereinafter referred is the refraction at spherical surface rate of laminate) of curved surface of polymer film of described laminate less than ± 0.5 diopter, and in the scope of the polymer film of removing form peripheral edge portions, maximum film thickness (W _Max) or minimum thickness (W _Min) and average film thickness (W _Av) between poor (Δ W=W _Max-W _AvOr W _Av-W _Min) be not more than 7% (Δ W/W _Av≤ 0.07).

Therefore, preparation in accordance with the present invention realizes solidifying effectively avoiding solution during curing to drip or inhomogeneous polymerization at short notice.Therefore, can on the curved surface of substrate, form the uniformly even photochromic coating of thickness.Therefore, the difference between the refraction at spherical surface rate of the refraction at spherical surface rate of substrate and laminate becomes less than ± 0.5 diopter.The high optical property that this expression can keep and almost not damage substrate and had.In addition, although be to form on curved surface, whole polymer film all has the thickness of homogeneous.The uniformity of thickness is very high, with average film thickness deviation be not more than 7% (Δ W/W _Av≤ 0.07).More easily form thickness homogeneous polymer film in the plane.But, use the routine techniques of coating film forming can not on curved surface, form even and thin polymer film.

Here, the refraction at spherical surface ability is represented the refracting power on a surface of glasses, and the index that can be used as the optical signature of estimating glasses is (by use as by Automation; RoboticsCo. Zhi Bei reflection-type curvature analyzer FOCOVISION SR-1 measures).Being expressed from the next is placed on as being positioned at the refraction at spherical surface ability F of the optical centre position of lens (substrate) in the air (refractive index is 1),

F＝(n-1)/r1

Wherein r1 is the radius of curvature (m) on a surface of lens, and n is the refractive index of lens.

When convex surface, described refraction at spherical surface ability F is for being negative value when the concave surface, and its unit is a diopter.By measuring the radius of curvature of the polymer film curved surface that forms, can be from the refraction at spherical surface ability of following formula computation layer compressing tablet.But in this article, the thickness of polymer film is less than the thickness of lens and can ignore.Therefore, refractive index n used herein is the refractive index of lens.

In addition, consider the true curved surface of substrate and the deviation of spherical shape, described refraction at spherical surface ability F can be expressed as " average surface refracting power ", because error source is not desirable sphere in the curved surface of substrate (as lens).Calculate the average surface refracting power according to following formula,

(refraction at spherical surface ability+cylinder refracting power) * 1/2

Available above-mentioned reflection-type curvature tester is measured described refraction at spherical surface ability or cylinder refracting power.The dioptric optical value of allowing based on the average surface refracting power of the laminate that is obtained by the present invention equates (less than ± 0.5 diopter) with the dioptric optical value of allowing based on the refraction at spherical surface ability.

When available bore hole is observed when containing wrinkle in the polymer film that forms on the substrate surface, the described refraction at spherical surface ability of energy measurement not just.Just, the surface reaction ability of energy measurement represent that described surface does not have can be by the observed wrinkle of bore hole.

Summary of drawings

Fig. 1 is for the schematic diagram of the method for coating photopolymerisable compositions, and in preparation method of the present invention, described photopolymerizable composition is adapted at forming on the substrate curved surface thickness for for example being not less than the photochromic coating of 10 μ m.

Fig. 2 is the enlarged diagram of the part of Fig. 1.

Implement the best approach of the present invention

Substrate

The lamination that the present invention uses the substrate of photochromic polymer film have curved surface, and be pressed with polymer film on described curved surface upper strata.The described surface of the representation of a surface of substrate has predetermined curvature.Though be not subjected to concrete restriction, if be expressed as spheric curvature 1/R, then preferred curvature is 1/R=1/0.05 to 1/1 (unit of R is rice).Can form curved surface on a surface or two surfaces of substrate.When two surfaces of substrate all are curved surface, polymer film can be laminated on two curved surfaces.Object lesson with substrate of curved surface comprises that two surfaces have the lens of same curvature, biconvex mirror, flat-concave mirror, convex meniscus lens, biconcave mirror and recessed meniscus lens.Specifically, can preferably use the two sides to have the convex meniscus lens and the recessed meniscus lens of same curvature, two kinds of lens all are widely used as glasses.In addition, preparation method of the present invention can prevent the substrate thermal deformation effectively.Therefore, when being not more than the thin substrate of 2mm, the center of curvature thickness that uses curved surface can obtain maximum effect.

The material that forms substrate is not particularly limited, can use following material: resin, for example (methyl) acrylic resin, polycarbonate resin, allyl resin, sulfo-polyurethane resin, polyurethane resin, thio epoxy, PETG, polypropylene, polyethylene, polystyrene, epoxy resin, polyvinyl chloride, polytetrafluoroethylene (PTFE) and organic siliconresin; Metal such as stainless steel (SUS), aluminium, copper and iron; Rubber is as styrene/butadiene rubbers, polybutadiene rubber, isoprene rubber and acrylic rubber; And any known material, as semiconductor, timber, unorganic glass, quartz glass, paper, pottery etc.But,, need to use substrate with transparency from giving the viewpoint of photochromic property.In order to prepare optical goods such as photochromic lens, described substrate is preferably glass or the resin that for example is used as lens usually.Plastic eyeglasses has curved surface usually.Because the progress of optical design in recent years, in many cases, described convex surface has complicated curved shape.Yet according to the present invention, this class is inhaled mirror and undoubtedly be can be used as substrate.

Photopolymerization and cured compositions

In the present invention, photopolymerization and the cured compositions that is used on the curved surface of substrate forming the photochromic polymer film comprises (A) free yl polymerizating monomer, (B) photochromic compound and (C) Photoepolymerizationinitiater initiater component.

(A) free yl polymerizating monomer

(A) do not have particular restriction to free yl polymerizating monomer, can use the known compound that has as the radical polymerization group of (methyl) acryloyl group, (methyl) acryloxy, vinyl, pi-allyl or styryl without restriction.Wherein, from the viewpoint that is easy to obtain and solidify, preferably use to have as (methyl) acryloyl group of radical polymerization group or the compound of (methyl) acryloxy.

In addition, as free yl polymerizating monomer, preferably unite and use high rigid monomer and low rigid monomer to improve the chemistry and the physical property of firming body, as solvent resistance, hardness and hear resistance and improvement photochromic property, as colour density and fade rates.

High rigid monomer is not less than the monomer of 60 L-scale Rockwell hardness for its homopolymers has, hang down rigid monomer is not more than 40 L-scale Rockwell hardness for its homopolymers has monomer.Measure L-scale Rockwell hardness according to JIS-B7726.The L-scale Rockwell hardness of the homopolymers by measuring described monomer can judge at an easy rate that high rigid monomer still is low rigid monomer.Specifically,, be allowed to condition at 25 ℃ indoor placement one day, obtain the thick firming body of 2mm, and use the rockwell hardness testing instrument to measure its L-scale Rockwell hardness, can determine monomer type easily like this by independent polymerization single polymerization monomer.But in this article, the polymer polymerization of determined its L-scale Rockwell hardness be no less than the polymerizable groups that 90% charging monomer is had.If polymerization be no less than 90% polymerizable groups, the general approximately constant value of L-scale Rockwell hardness of then determined firming body.

High rigid monomer can improve solvent resistance, hardness and the hear resistance of curing materials (polymer film).In order to highlight above-mentioned effect, the L-scale Rockwell hardness that preferably uses its homopolymers is 65 to 130 high rigid monomer.

The rigid monomer of this height is the compound that has 2 to 15 on the molecule and be more preferably 2 to 6 free redical polymerization groups.The example comprises that hereinafter formula (1) is to the compound of formula (5) expression.The number of repeat unit of the repetitive on the compound main chain that is expressed from the next has certain limit, allows to use the mixture of the multiple molecule with different repeat units number as the rigid monomer of height.

Wherein, R ¹Be hydrogen atom or methyl, R ²Be hydrogen atom, methyl or ethyl, R ³Be organic residue of 3 to 6 valencys, f is 0 to 3 integer, and f ' is 0 to 3 integer, and g is 3 to 6 integer,

Wherein, R ⁴Be hydrogen atom or methyl, B is the organic residues of 3 valencys, and D is the organic residue of divalent, and h is 1 to 10 integer,

Wherein, R ⁵Be hydrogen atom or methyl, R ⁶Be hydrogen atom, methyl, ethyl or hydroxyl, E is the organic residue of divalence with ring, and i and j be positive integer or 0, makes that the mean value of i+j is 0 to 6,

Wherein, R ⁷Be hydrogen atom or methyl, F be for having 2 to 9 carbon atoms with alkylidene and its main chain of side chain,

Wherein, R ⁸Be hydrogen atom, methyl or ethyl, and k is 1 to 6 integer.

Can be clear that by following formula (1) to (5), wherein R ¹, R ⁴, R ⁵And R ⁷Be hydrogen atom or methyl, therefore the compound by the following formula representative is the compound with 2 to 6 (methyl) acryloxies.When containing these a large amount of groups in the molecule, most of groups can differ from one another.But from the viewpoint that is easy to get, preferred most of groups are identical, and (this point is to hereinafter with the R that occurs ¹¹And R ¹⁴Also be suitable for).

In following formula (1), R ²Be hydrogen atom, methyl or ethyl, R ³It is organic residue of 3 to 6 valencys.Organic residue is had no particular limits, and main chain also can comprise the key as ester bond, ehter bond, amido link, thioether bond, sulphonyl key or ammonia ester bond (urethane bond) except that being the carbon-carbon bond.Be not less than 60 L-scale Rockwell hardness, R in order to allow described homopolymers have ³Be preferably organic residue, more preferably have organic residue of 1 to 15 carbon atom and can comprise ehter bond and/or ammonia ester bond with 1 to 30 carbon atom.

In formula (1), f and f ' also can be 0 to 3 integer independently of one another.When f or f ' are not less than 3, the homopolymers of described monomer will have and be not more than 60 L-scale Rockwell hardness.In order to allow L-scale Rockwell hardness be not less than 60, f and f ' and be preferably 0 to 3.

Example by the high rigid monomer of formula (1) representative comprises trimethylol-propane trimethacrylate, trimethylolpropane triacrylate, the tetramethylol methane trimethyl acrylic ester, the tetramethylol methane triacrylate, trimethylol-propane trimethacrylate, tetramethylol methane tetramethyl acrylate, the tetramethylol methane tetraacrylate, trimethylolpropane tris glycol trimethyl acrylic ester, trimethylolpropane tris glycol triacrylate, the ethoxylation tetramethylol methane tetraacrylate, ethoxylation pentaerythrite tetramethyl acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, dipentaerythritol acrylate, the urethane oligomer tetraacrylate, urethane oligomer hexamethyl acrylate, urethane oligomer six acrylate, polyester oligomer six acrylate, the dipentaerythritol acrylate of caprolactone modification and two (trimethyl) propane tetraacrylate.

In formula (2), B is that organic residue of 3 valencys and D are the organic residue of divalent.Organic residue B and D are not had particular restriction, outside main chain de-carbon-carbon bond, also can comprise key as ester bond, ehter bond, amido link, thioether bond, sulphonyl key or ammonia ester bond.For being had, described homopolymers is not less than 60 L-scale Rockwell hardness, B is preferably the organic residue that is derived from the straight or branched hydrocarbon with 3 to 10 carbon atoms, and D is preferably and is derived from organic residue of straight or branched aliphatic hydrocarbon with 1 to 10 carbon atom or the organic residue that is derived from the aromatic hydrocarbons with 6 to 10 carbon atoms.

In the compound of formula (2), for being had, described homopolymers is not less than 60 L-scale Rockwell hardness, and h is preferably 1 to 10 integer, particularly 1 to 6 integer.

Example by the high rigid monomer of following formula (2) representative comprises that molecular weight is 2,500 to 3, polyester oligomer (the EB80 of 500 four-functional group, by DAICEL UCB COMPANY LTD. preparation), molecular weight is 6,000 to 8, polyester oligomer (the EB450 of 000 four-functional group, by DAICEL UCB COMPANY LTD. preparation), molecular weight is 45,000 to 55, the polyester oligomer of 000 six functional groups (EB1830 is by DAICEL UCB COMPANY LTD. preparation), molecular weight is the polyester oligomer (GX8488B of 10,000 four-functional group, by Dai-ichi Kogyo Seiyaku Co., the Ltd. preparation).

In following formula (3), R ⁶Be hydrogen atom, methyl, ethyl or hydroxyl, and E is the organic residue of divalence of band shape structure.As long as described organic residue E has circulus, it there is not other particular restriction.In addition, outside main chain de-carbon-carbon bond, also can comprise key as ester bond, ehter bond, amido link, thioether bond, sulphonyl key or ammonia ester bond.The example of the ring of organic residue E comprises phenyl ring, cyclohexane ring, adamantane ring and ring as follows:

In the present invention, the ring of organic residue E is preferably phenyl ring, and preferred organic residue E is shown below:

Wherein G is that oxygen atom, sulphur atom or any are selected from-S (O ₂)-,-C (O)-,-CH ₂-,-CH=CH-,-C (CH ₃) ₂-and-C (CH ₃) (C ₆H ₅)-group, R ⁹And R ¹⁰Independently of one another for having the alkyl or the halogen atom of 1 to 4 carbon atom, and l and l ' are 0 to 4 integer independently of one another.

In the present invention, most preferred organic residue E is shown below:

In formula (3), i and j are positive integer or 0, and the mean value of i+j is 0 to 6.The compound by formula (3) representative that generally obtains is the mixture of multiple compound, and except i and j were 0 situation, i and j were differing from each other.With a large amount of compounds separated from each other be difficult, therefore i and j are expressed as the mean value of i+j.More preferably the mean value of i+j is 2 to 6.

Examples for compounds by formula (3) expression comprises bisphenol A-type dimethylacrylate, 2, two (the 4-methacryloxy ethoxyl phenenyl) propane and 2 of 2-, two (3, the 5-two bromo-4-methacryloxy ethoxyl phenenyls) propane of 2-.

In formula (4), R ⁷Be hydrogen atom or methyl, F is for having 2 to 9 carbon atoms with alkylidene and its main chain of side chain.The example that main chain has the alkylidene of 2 to 9 carbon atoms comprises ethylidene, propylidene, 1,3-propylidene, butylidene, inferior neopentyl, hexylidene and inferior nonyl.When the carbon number of chain surpasses 9, described homopolymers will have and be not more than 60 L-scale Rockwell hardness.

Examples of compounds by formula (4) expression comprises glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethylacrylate, 1,9-nonanediol dimethylacrylate, neopentylglycol dimethacrylate and neopentylglycol diacrylate.

In formula (5), R ⁸Be hydrogen atom, methyl or ethyl, and k is 1 to 6 integer.When k surpasses 6, described homopolymers will have and be not more than 60 L-scale Rockwell hardness.Preferred k is 3 or 4.

Comprise diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethylacrylate and the three four propane diols dimethylacrylates that contract by the examples of compounds of formula (5) expression.

Can use described free yl polymerizating monomer (high rigid monomer) separately or use the mixture of several monomers, the homopolymers of wherein said monomer can have and is not less than 60 L-scale Rockwell hardness.

In the compound of following formula (1) to (5) representative, the homopolymers of some monomers can have L-scale Rockwell hardness less than 60 according to substituent combined situation.In this case, described compound can be classified as low rigid monomer or as mentioned below in rigid monomer.

Except compound by following formula (1) to (5) representative, also have other high rigid monomer, their exemplary examples comprise bisphenol A-type diglycidyl methacrylate, ethylene glycol bisthioglycolate glycidyl methacrylate and GMA.

Described low rigid monomer (its homopolymers have be not more than 40 L-scale Rockwell hardness) can be united use with toughness reinforcing to the material (polymer film) that solidifies and improve the fade rates of the photochromic compound that exists in the polymer film with the rigid monomer of above-mentioned height.

As low rigid monomer, can for example the monomer of the simple function group of representing by the monomer of the difunctional of following formula (6) and (7) expression and by following formula (8) and (9) is arranged,

Wherein, R ¹¹Be hydrogen atom or methyl, R ¹²And R ¹³Be hydrogen atom, methyl or ethyl independently of one another, Z is oxygen atom or sulphur atom, works as R ¹¹During for hydrogen atom, m is 1 to 70 integer and works as R ¹¹During for methyl, m is 7 to 70 integer, and m ' is 0 to 70 integer,

Wherein, R ¹⁴Be hydrogen atom or methyl, R ¹⁵And R ¹⁶Be hydrogen atom, methyl, ethyl or hydroxyl independently of one another, I is the organic residue of divalence of band shape structure, and i ' and j ' are integer, and the mean value of i '+j ' is 8 to 40,

Wherein, R ¹⁷Be hydrogen atom or methyl, R ¹⁸And R ¹⁹Be hydrogen atom, methyl or ethyl independently of one another, R ²⁰For hydrogen atom, the alkyl with 1 to 25 carbon atom, alkenyl, alkoxyalkyl, haloalkyl, have the aryl of 6 to 25 carbon atoms, or have the acyl group [not comprising (methyl) acryloyl group] of 2 to 25 carbon atoms, Z is oxygen atom or sulphur atom, works as R ¹⁷During for hydrogen atom, m " be 1 to 70 integer and work as R ¹⁷During for methyl, m " be 4 to 70 integer, m " ' be 0 to 70 integer,

Wherein, R ²¹For hydrogen atom or methyl, work as R ²¹During for hydrogen atom, R ²²For have 1 to 20 carbon atom alkyl and work as R ²¹During for methyl, R ²²For having the alkyl of 8 to 40 carbon atom.

At following formula (6) in (9), R ¹¹, R ¹⁴, R ¹⁷And R ²¹Be hydrogen atom or methyl.Just, low rigid monomer generally has the polymer-based group of no more than two (methyl) acryloxies or (methyl) acryloyl sulfenyl.

In formula (6), R ¹²And R ¹³Be hydrogen atom, methyl or ethyl independently of one another, and Z is oxygen atom or sulphur atom.

In the compound of formula (6), work as R ¹¹During for hydrogen atom, just, when described compound had the polymer-based group of acryloxy or acryloyl sulfenyl, m was 7 to 70 integer, and worked as R ¹³During for methyl, just, when described compound had the polymer-based group of methacryloxy or methacryl sulfenyl, m was 1 to 70 integer.In addition, m ' is 0 to 70 integer.

Instantiation by the low rigid monomer of formula (6) representative comprises that aklylene glycol two (methyl) acrylate is as three aklylene glycol diacrylates, four aklylene glycol diacrylates, nonyl aklylene glycol diacrylate and nonyl aklylene glycol dimethylacrylate.

In formula (7), R ¹⁴Be hydrogen atom, methyl or ethyl, and I is the organic residue of divalence of band shape structure.As described organic residue I, the example that can enumerate is identical with the organic residue of divalence of following formula (3) band shape structure.In formula (7), it is 8 to 40 that i ' and j ' also can be the mean value that makes i '+j ', is preferably 9 to 30 integer.For with following formula (3) in the integer i reason identical with j, generally also integer i ' and j ' are expressed as mean value.

By the low rigid monomer of formula (7) expression comprise mean molecule quantity be 776 2,2-pair of (4-acryloxy polyethylene glycol phenyl) propane etc.

In formula (8), R ¹⁷Be hydrogen atom or methyl, and R ¹⁸And R ¹⁹Be hydrogen atom, methyl or ethyl independently of one another.R ²⁰For hydrogen atom, the alkyl with 1 to 25 carbon atom, alkenyl, alkoxyalkyl, haloalkyl, have the aryl of 6 to 25 carbon atoms or the acyl group except that acryloyl group with 2 to 25 carbon atoms.

As alkyl or alkenyl with 1 to 25 carbon atom, the example that can enumerate has methyl, ethyl, propyl group and nonyl.Described alkyl or alkenyl can be the straight or branched group, and can have the substituting group as halogen atom, hydroxyl, aryl or epoxy radicals.

As the alkoxyalkyl with 1 to 25 carbon atom, the example that can enumerate has methoxyl group butyl, ethyoxyl butyl, butoxy butyl and methoxyl group nonyl.

As the aryl with 6 to 25 carbon atoms, the example that can enumerate has phenyl, toluyl groups, anthryl and octyl phenyl.As the acyl group except that (methyl) acryloyl group, the example that can enumerate has acetyl group, propiono, bytyry, valeryl and oleoyl.

In the compound of formula (8), work as R ¹⁷During for hydrogen atom, just, when described compound has the polymer-based group of acryloxy or acryloyl sulfenyl, m " be 1 to 70 integer and work as R ¹⁷During for methyl, just, when described compound has the polymer-based group of methacryloxy or methacryl sulfenyl, m " be 4 to 70 integer.In addition, m  is 0 to 70 integer.

Instantiation by the low rigid monomer of formula (8) representative comprises that PAG (methyl) acrylate such as mean molecule quantity are 526 polyethylene glycol methacrylate-styrene polymer, mean molecule quantity is 360 polyethylene glycol methacrylate-styrene polymer, mean molecule quantity is 475 methyl ether polyethylene glycol methacrylate-styrene polymer, mean molecule quantity is 1000 methyl ether polyethylene glycol methacrylate-styrene polymer, mean molecule quantity is 375 polypropylene glycol methacrylate, mean molecule quantity is 430 polypropylene glycol methacrylate, mean molecule quantity is 622 polypropylene glycol methacrylate, mean molecule quantity is 620 methyl ether polypropylene glycol methacrylate, mean molecule quantity is 566 polytetramethylene glycol methacrylate, mean molecule quantity is 2,034 octyl phenyl ether polyethylene glycol methacrylate-styrene polymer, mean molecule quantity is 610 nonyl ethers polyethylene glycol methacrylate-styrene polymer, mean molecule quantity is that poly-dithioglycol methacrylate of 640 methyl ether and mean molecule quantity are 498 perfluor heptyl glycolmethacrylate.

In formula (9), R ²¹Be hydrogen atom or methyl, and work as R ²¹During for hydrogen atom, R ²²For having the alkyl of 1 to 20 carbon atom, work as R ²¹During for methyl, R ²²For having the alkyl of 8 to 40 carbon atoms.

Described alkyl can be the group of straight or branched, and can have the substituting group as halogen atom, hydroxyl, alkoxyl, acyl group or epoxy radicals.

Instantiation by the low rigid monomer of formula (9) representative comprises methacrylic acid octadecane ester, lauryl methacrylate, methacrylic acid ethylhexyl, methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate.

In the present invention, homopolymers can be had the low rigid monomer and the rigid monomer of above-mentioned height that are not more than 40 L-scale Rockwell hardness and unite use, perhaps two or more low rigid monomers and the rigid monomer of above-mentioned height can be united use.In low rigid monomer by following formula (6) to (9) expression, especially preferably using mean molecule quantity is that 475 methyl ether polyethylene glycol methacrylate-styrene polymer, mean molecule quantity are 1,000 methyl ether polyethylene glycol methacrylate-styrene polymer, three aklylene glycol diacrylates, four aklylene glycol diacrylates, nonyl aklylene glycol diacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate.

In the compound by following formula (6) to (9) expression, the homopolymers of some compound can be dependent on substituent combination and has and be not less than 40 L-scale Rockwell hardness.But, this compound can classify as the rigid monomer of above-mentioned height or hereinafter will describe in rigid monomer.

In the present invention in photopolymerization of Shi Yonging and the cured compositions, allow to use the free yl polymerizating monomer except that rigid monomer of above-mentioned height or low rigid monomer, just, rigid monomer in rigid monomer of height and low rigid monomer use, in these homopolymers of rigid monomer can demonstrate be not less than 40 but be not more than 60 L-scale Rockwell hardness.In the example of rigid monomer comprise the monomer of free redical polymerization simple function group, just, (methyl) acrylate of difunctional such as mean molecule quantity are that 650 polytetramethylene glycol dimethylacrylate, mean molecule quantity are polytetramethylene glycol dimethylacrylate and two (2-dimethyl allene acyl-oxygen ethylenebis dithiocarbamate ethyl) thioethers of 1,400; Multivalence allyl compound such as diallyl phthalate, DAIP, tartaric acid diallyl, epoxy succinic diallyl phthalate, diallyl fumarate, diallyl chlorendate, hexahydrophthalic acid diallyl (diallylhexaphthalate) and allyl diglycol carbonates; Multivalence sulfo-acrylate compounds and multivalence sulphomethyl acrylate compounds, as 1, two (methacryl sulfenyl) ethane of 2-, two (2-acryloyl sulfenyl ethyl) ether and 1, two (the methacryl sulfenyl methyl) benzene of 4-; Unsaturated carboxylic acid such as acrylic acid, methacrylic acid and maleic anhydride; Acrylate compounds and methacrylate compound, for example methyl methacrylate, butyl methacrylate, benzyl methacrylate, phenyl methacrylate, methacrylic acid 2-hydroxyl ethyl ester and methacrylic acid biphenyl ester; Fumarate compound such as DEF and fumaric acid diphenyl ester; Sulfo-acrylate compounds and sulphomethyl acrylate compounds be first acrylic acid methyl mercaptan ester, acrylic acid benzyl mercaptan ester and methacrylic acid benzyl mercaptan ester for example; Vinyl compound is styrene, chlorostyrene, methyl styrene, vinyl naphthalene, AMS dimer, bromstyrol, divinylbenzene and vinyl pyrrolidone for example; And have (methyl) acrylate that contains 6 to 25 carbon atoms in unsaturated bond and the hydrocarbon chain in the molecule, as methacrylic acid oleyl alcohol ester, methacrylic acid flores aurantii alcohol ester, methacrylic acid spiceleaf alcohol ester, methacrylic acid linalool ester and methacrylic acid Acacia alcohol ester.

In the present invention, in order to keep good balance between solvent resistance, hardness, hear resistance and the photochromic property of firming body (photochromic polymer film) such as colour density and fade rates, preferred described free yl polymerizating monomer (A) comprises the low rigid monomer of 5 to 70% weight and the high rigid monomer of 5 to 95% weight.In addition, preferably with described free yl polymerizating monomer be no less than the high rigid monomer that having of 5% weight be no less than three radical polymerization groups and mix.

Except the monomer according to hardness classification as mentioned above, also need free yl polymerizating monomer (A) is mixed use with the free yl polymerizating monomer (hereinafter referred is an epoxy monomer) that has at least one epoxy radicals and at least one radical polymerization group in molecule.Use epoxy monomer can improve the light resistance of photochromic compound and further promote described substrate and described photochromic polymer film (coating) between cohesive.The homopolymers of epoxy monomer can demonstrate according to its structure and be not less than 60 or be not more than 40 L-scale Rockwell hardness.If according to the classification of the hardness of described homopolymers, can according to hardness with its classify as high rigid monomer, low rigid monomer or in the rigid monomer any.

As described epoxide, can use compound known.But, preferably use to have the compound of (methyl) acryloxy as the radical polymerization group.Specifically, can use the compound of representing by following formula (10):

Wherein, R ²³And R ²⁶Be hydrogen atom or methyl independently of one another, R ²⁴And R ²⁵Independently of one another for having the alkylidene of 1 to 4 carbon atom or the group that is expressed from the next:

Wherein, G ' is oxygen atom, sulphur atom or is selected from-S (O ₂)-,-C (O)-,-CH ₂-,-CH=CH-,-C (CH ₃) ₂-and-C (CH ₃) (C ₆H ₅)-any group, R ²⁷And R ²⁸Independently of one another for having the alkyl or the halogen atom of 1 to 4 carbon atom, and l " and l  be 0 to 4 integer independently of one another,

S and t are 0 to 20 integer independently of one another.

In formula (10), by R ²⁴And R ²⁵The alkylidene with 1 to 4 carbon atom of expression comprises methylene, ethylidene, propylidene, 1,3-propylidene and butylidene.In addition, alkylidene also can have hydroxyl or halogen atom substituting group.

Work as R ²⁴Or R ²⁵For by the group of following formula (10a) expression the time, G ' is oxygen atom, sulphur atom or is selected from-S (O ₂)-,-C (O)-,-CH ₂-,-CH=CH-,-C (CH ₃) ₂-or-C (CH ₃) (C ₆H ₅)-any group.In formula (10a), R ²⁷And R ²⁸For having the alkyl of 1 to 4 carbon atom,, perhaps be halogen atom independently of one another,, l as chlorine atom or bromine atoms as methyl, ethyl, propyl group or butyl " and l  be 0 to 4 integer independently of one another.Most preferably the group by formula (10a) expression is a kind of group that is expressed from the next:

Instantiation by the epoxy monomer of formula (10) expression comprises glycidyl acrylate, GMA, methacrylic acid Beta-methyl ethylene oxidic ester, bisphenol A-type-methacrylic acid one glycidol ether-ether, 4-glycidyl oxygen base acrylate, 3-(glycidyl-2-oxygen base oxethyl)-2-hydroxypropyl methyl acrylate, 3-(glycidyl Oxy-1-isopropoxy)-2-hydroxypropyl acrylate, 3-(glycidyl oxygen base-2-hydroxyl propoxyl group)-2-hydroxypropyl acrylate and mean molecule quantity are 540 glycidyl oxygen base polyethylene glycol methacrylate-styrene polymer.Wherein preferred especially glycidyl acrylate, GMA and mean molecule quantity are 540 glycidyl oxygen base polyethylene glycol methacrylate-styrene polymer.

Preferably with described free yl polymerizating monomer (A) and described epoxy monomer with 0.01 to 30% weight, the ratio of preferred especially 0.1 to 20% weight is mixed.

For the hardness that improves the photochromic polymer film or improve it and the cohesive of substrate (as glasses), can be with the rigid monomer of above-mentioned height and low rigid monomer with the band silanol or form free yl polymerizating monomer (hereinafter the being commonly referred to as isocyanate-monomer) use of the free yl polymerizating monomer (hereinafter being commonly referred to as silyl group monomer) or the band NCO of silanol by hydrolysis.

As described silyl group monomer, can use various known compounds without restriction, as long as these compounds have silanol or form silanol and radical polymerization group by hydrolysis.

In silyl group monomer, the instantiation that forms the group of silanol group by hydrolysis comprises alkoxysilyl (≡ Si-O-R; R is an alkyl), aryloxymethyl silylation (≡ Si-O-Ar; Ar is commutable aryl), halo silicyl (≡ Si-X; X is a halogen atom), siloxy silicyl (disiloxane key; ≡ Si-O-Si ≡).From being easy to form silanol, being easy to synthesize and preserving and from the isolated group of the silicon atom viewpoint very little, preferably use alkoxysilyl or siloxy silicyl to the firming body Effect on Performance owing to react.More preferably use the alkoxysilyl of alkoxyl, and most preferably use methoxy methyl silylation or (ethoxymethyl) silylation with 1 to 4 carbon atom.

As the described radical polymerization group that has of silyl group monomer, the example that can enumerate has (methyl) acryloyl group; Derived from the group of (methyl) acryloyl group, as (methyl) acryloxy, (methyl) acrylamido and (methyl) acryloyl sulfenyl; And known radical polymerization group, as vinyl, pi-allyl and styryl.When described radical polymerization group was vinyl, pi-allyl or styryl, described radical polymerization group can have substituting group.As described substituting group, the example that can enumerate has the alkyl with 1 to 4 carbon atom, as methyl, ethyl, propyl group, butyl, chloromethyl, trifluoromethyl, or haloalkyl, halogen atom, cyano group, nitro and hydroxyl.When described radical polymerization group is (methyl) acrylamido, the nitrogen-atoms of the acylamino-of described group can with following group bonding: (methyl) acryloyl group; Silanol group, hydrolysis forms the group of silanol group; Organic group is as alkyl, aryl or the pi-allyl of replacement or non-replacement.

In these radical polymerization groups, from being easy to get and the viewpoint of polymerization, preferred acryloyl group or (methyl) acryloxy, and more preferably (methyl) acryloxy.

In the present invention, preferred silyl group monomer is the monomer by following formula (11) to (13) expression:

Wherein, R ²⁹Be alkyl or aryl, R ³⁰And R ³¹Be alkyl, aryl or acyl group independently of one another, A is organic residue of 2 to 4 valencys, and Y is the radical polymerization group, and a is 1 to 3 integer, and b is 0 to 2 integer, and c is 0 to 2 integer, and d is 1 to 3 integer, and e is 1 to 3 integer, but a+b+c+d=4,

Wherein, R ³⁰And R ³¹Be alkyl, aryl or acyl group independently of one another, A is organic residue of 2 to 4 valencys, and Y is the radical polymerization group, and b is 0 to 2 integer, and c is 0 to 2 integer, and d is that 1 to 3 integer and e are 1 to 3 integer, but b+c+d=3,

Wherein, R ²⁹Be alkyl or aryl, R ³⁰And R ³¹Be alkyl, aryl or acyl group independently of one another, R ³²Be vinyl, a is 1 to 3 integer, and b is 0 to 2 integer, and c is 0 to 2 integer, and d is 1 to 3 integer, but a+b+c+d=4,

In formula (11) in (13), R ²⁹Be alkyl or aryl, from being easy to generate the viewpoint of silanol and stable storage by hydrolysis, be preferably and replace or alkyl non-replacement, that 1 to 10 carbon atom is arranged on the main chain, or for replacing or aryl non-replacement, that 6 to 10 carbon atoms are arranged on the ring.The substituent example of alkyl or aryl comprises the alkyl with 1 to 10 carbon atom, as methyl, ethyl and propyl group; Haloalkyl with 1 to 10 carbon atom is as chloromethyl and trifluoromethyl; Alkoxyl with 1 to 10 carbon atom is as methoxyl group, ethyoxyl and butoxy; Acyl group with 2 to 10 carbon atoms is as acetyl group, propiono, oleoyl and benzoyl; Amino; Amino with alkyl replacement of 1 to 10 carbon atom is as methylamino, ethylamino, dimethylamino and diethylamino; Halogen atom, for example fluorine atom, chlorine atom and bromine atoms; Hydroxyl; Carboxyl; Sulfydryl; Cyano group; And nitro.In the present invention, radicals R ²⁹Preferred example comprise methyl, ethyl, propyl group, butyl, chloromethyl, phenyl, toluyl and xylyl.From being easy to generate by hydrolysis the viewpoint of silanol and stable storage, most preferred example comprises alkyl, particularly methyl or the ethyl with 1 to 4 carbon atom.

In formula (11) in (13), R ³⁰And R ³¹Be alkyl, aryl or acyl group independently of one another.As described alkyl and aryl, the group that can give an example is and R ²⁹Those identical groups of description, and preferred alkyl and aryl are and R ²⁹Those identical groups of description.That described acyl group can be aliphatic series or the acyl group of aromatics, and more preferred example is the acyl group with 2 to 10 carbon atoms, as acetyl group, propiono and benzoyl.

In (12), A also is organic residue of 2 to 4 valencys in formula (11).Structure to organic residue A does not have particular restriction, can have side chain and substituting group.In addition, also can be outside de-carbon-carbon bond in its structure just like ehter bond, ester bond, amido link, ammonia key, ammonia ester bond, thioether bond or sulphonyl key.Wherein also can comprise ketone group (ketone carbon).The substituent example that organic residue A can have comprises halogen atom such as fluorine atom, chlorine atom and bromine atoms, and hydroxyl, amino, sulfydryl, cyano group and nitro.

In (12), described organic residue A also preferably has 1 to 30 carbon atom in formula (11), preferred especially 1 to 10 carbon atom.The example of preferred organic residue A comprises the alkylidene with 1 to 10 carbon atom, as methylene, ethylidene, propylidene, 1,3-propylidene and butylidene, alkylenedioxy group with 1 to 10 carbon atom, as methylene-dioxy, ethylenedioxy, the inferior third dioxy base and Aden's dioxy base, and the group that is expressed from the next:

Wherein n is 1 to 5 integer, and n ' and n " be 1 to 3 integer.

Above illustrative preferred organic residue A can have above-mentioned substituting group.

In formula (11) in (12); Y is that radical polymerization group and its example comprise (methyl) acryloyl group and derived from the group of (methyl) acryloyl group; for example (methyl) acryloxy, (methyl) acrylamido and (methyl) acryloyl sulfenyl, and the styryl of the pi-allyl of the vinyl of replacement or non-replacement, replacement or non-replacement and replacement or non-replacement.Preferred example comprises (methyl) acryloyl group and (methyl) acryloxy.

Example by the silyl group monomer of following formula (11) to (13) representative comprises γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl methyl dimethoxysilane, (3-acryloxy propyl group) dimethyl methyl TMOS, (3-acryloxy propyl group) methyl dimethoxysilane, (3-acryloxy propyl group) trimethoxy silane, 3-(N-allyl amino) propyl trimethoxy silicane, the allyl dimethyl TMOS, allyltriethoxysilane, allyltrimethoxysilanis, 3-amino-benzene oxygen dimethyl vinyl silanes, 4-amino-benzene oxygen dimethyl vinyl silanes, 3-(the amino propoxyl group of 3-)-3,3-dimethyl-1-acrylic trimethoxy silane, the cyclobutenyl triethoxysilane, 2-(chloromethyl) allyltrimethoxysilanis, the diethoxy vinyl silanes, 1,3-divinyl tetraethoxy disiloxane, the dococenyl triethoxysilane, neighbour-(methacryloxyethyl)-N-(triethoxysilylpropyltetrasulfide) urethanes, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxywerene werene, the methacryloxy ethoxytrimethylsilane, (methacryloxy methyl) dimethylethoxysilane, the methacryloxy MTES, the methacryloxy MTMS, the methacryloxypropyl dimethylethoxysilane, methacryloxypropyl dimethyl methyl TMOS, methacryloxypropyl three (methoxy ethoxy) silane, 7-octenyl trimethoxy silane, 1, two (the methacryloxy)-2-trimethoxy propane of 3-, four (2-methacryloxy ethyoxyl) silane, the trivinyl Ethoxysilane, the trivinyl methoxy silane, vinyl-dimethyl base oxethyl silane, vinyl diphenyl Ethoxysilane, vinyl methyl diacetoxyl silane, the vinyl methyldiethoxysilane, the vinyl methyl dimethoxysilane, neighbour-(vinyl oxygen base ethyl)-N-(triethoxysilylpropyltetrasulfide) carbamate, vinyl oxygen base trimethyl silane, the ethenylphenyl diethoxy silane, ethenylphenyl methyl methoxy base silane, vinyl triacetic acid base silane, vinyl three-tert-butoxy silane, VTES, vinyl three different propenyloxy group (isopropenoxy) silane, vinyl silane triisopropoxide, vinyltrimethoxy silane, vinyl triple phenoxyl silane and vinyl three (2-methoxy ethoxy) silane.These silyl group monomer can be used separately or two or three unite use.

Above-mentioned according to silyl group monomer of the present invention in, the preferred silyl group monomer of using by formula (11) expression.Wherein, the preferred especially silyl group monomer of using by following formula (14) expression:

Wherein, R ³³Be hydrogen atom or methyl, R ³⁴For having the alkylidene of 1 to 10 carbon atom, R ³⁵For having the alkoxyl of 1 to 4 carbon atom, R ³⁶For having the alkyl of 1 to 4 carbon atom, a ' is 1 to 3 integer, and b ' is 0 to 2 integer, but a '+b '=3.

As the alkylidene R that has 1 to 10 carbon atom in the following formula (14) ³³, the example that can enumerate has ethylidene, propylidene, 1,3-propylidene and butylidene.As alkoxyl R with 1 to 4 carbon atom ³⁵, the example that can enumerate has methoxyl group, ethyoxyl, propoxyl group and butoxy.As alkyl R with 1 to 4 carbon atom ³⁶, the example that can enumerate has methyl, ethyl, propyl group and butyl.

Instantiation by the silyl group monomer of formula (14) expression comprises γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, (3-acryloxy propyl group) dimethyl methyl TMOS, (3-acryloxy propyl group) methyl dimethoxysilane, (3-acryloxy propyl group) trimethoxy silane, (methacryloxy methyl) dimethylethoxysilane, the methacryloxy MTES, the methacryloxy MTMS, methacryloxypropyl dimethylethoxysilane and methacryloxypropyl dimethyl methyl TMOS.

In the present invention, isocyanate-monomer can replace above-mentioned silyl group monomer use or with silyl group monomer use with raising and substrate and with the cohesive of hard coating material.

As isocyanate-monomer,, (NCO) all can use without restriction any compound with the radical polymerization group as long as having isocyanate groups.For example, can use the compound of representing by following formula (15) to (16):

R wherein ³⁷Be hydrogen atom or methyl and R ³⁸Be alkylidene,

R wherein ³⁹Be hydrogen atom or methyl and R ⁴⁰Be alkylidene.

At following formula (15) in (16), R ³⁸And R ⁴⁰All be alkylidene, and be preferably alkylidene especially, as methylene, ethylidene, propylidene, 1,3-propylidene or butylidene with 1 to 10 carbon atom.

In the present invention, the instantiation of the preferred isocyanate-monomer that uses comprises 2-isocyanato-ethoxyl methyl acrylate, 4-(2-isocyanato-isopropyl) styrene etc.Above-mentioned isocyanate-monomer can use separately or two or more use together.Combined amount to silyl group monomer and isocyanate-monomer is not particularly limited.Yet, for improve with substrate such as glasses and with the cohesive of the hard coating layer that on polymer film, forms, the mixing total amount of preferred described silyl group monomer or described isocyanate-monomer accounts for 0.5 to 20% weight of free yl polymerizating monomer total amount, preferred 1 to 10% weight.When consumption very little the time, be difficult to promote polymer film and substrate and and hard coating layer between cohesive.On the contrary, when consumption was too big, except that the photochromic property such as colour density and fade rates reduction of polymer film, the wearability of the hard coating layer that forms on polymer film also descended.

In the present invention, when with above-mentioned silyl group monomer or isocyanate-monomer during, photopolymerization and cured compositions need be mixed with amines as catalyst as free yl polymerizating monomer.After described amines mixes, can greatly improve the cohesive between polymer film (material that composition solidify to form) and the substrate and greatly improve cohesive between polymer film and the hard conating.

As described amines, can use any without restriction as above-mentioned silyl group monomer or the condensation of isocyanate-monomer or the known alkaline amines of addition catalyst.In this article, the hindered amine compound that only has the amino that is expressed from the next does not have above-mentioned catalysis, and it will be got rid of from the amines of indication above:

R wherein ⁴¹Be hydrogen atom or alkyl, R ⁴², R ⁴³, R ⁴⁴And R ⁴⁵Be identical or different alkyl.

The instantiation of the preferred amines that uses comprises the not low molecular amine compound of polymerizable in the present invention, as triethanolamine, N methyldiethanol amine, triisopropanolamine, 4, and 4-dimethylamino benzophenone and two azo double-octanes; Amines with polymerizable groups, as methacrylic acid N, N-dimethyl aminoethyl ester and methacrylic acid N, N-diethylamino ethyl ester; And the amines of band silicyl, as N-(ethoxy)-N-methylamino propyl trimethoxy silicane, Dimethoxyphenyl-2-piperidino Ethoxysilane, N, N-diethylamino methyl trimethyl silane and (N, N-diethyl-3-aminopropyl) trimethoxy silane.These amines can use separately or two or more use together.

In above-mentioned amines,, preferably especially use amines hydroxyl, maybe can form the group of silanol as (methyl) acryloxy of radical polymerization group by hydrolysis from improving fusible viewpoint.These amines can be represented by for example following formula (17):

R wherein ⁴⁶For hydrogen atom or have the straight chained alkyl of 1 to 4 carbon atom, R ⁴⁷For hydroxyl, (methyl) acryloxy maybe can form the group of silanol, R by hydrolysis ⁴⁸For hydrogen atom or have the alkyl of 1 to 6 carbon atom, hydroxyl, (methyl) acryloxy maybe can form the group of silanol by hydrolysis, and A ' works as R for having the alkylidene of 2 to 6 carbon atoms ⁴⁸During for hydrogen atom or alkyl, A " for having the alkylidene of 1 to 6 carbon atom, work as R ⁴⁸In the time of maybe forming the group of silanol for hydroxyl, (methyl) acryloxy by hydrolysis, A " for having the alkylidene of 2 to 6 carbon atoms.

When above-mentioned amines is highly basic, can improve cohesive most effectively, therefore for the present invention most preferably.Can form the R of silanol by hydrolysis ⁴⁷And R ⁴⁸Be those identical groups that above silyl group monomer defined.

The mixing consumption of above-mentioned amines is: the total free yl polymerizating monomers of per 100 weight portions (A) use 0.01 to 20 weight portion, preferred 0.1 to 10 weight portion, more preferably 1 to 10 weight portion.When consumption is less than 0.01 weight portion or surpasses 20 weight portions, can not improve the cohesive between photochromic polymer film and the substrate, in addition, when consumption surpassed 20 weight portions, the photochromic polymer film was with yellowing, and this does not wish to take place.

(B) photochromic compound

According to the present invention,, must in described photopolymerization and cured compositions, mix the photochromic compound of 0.2 to 20% weight in order to give the polymer film that on the substrate curved surface, forms photochromic property.Like this, have very little thickness, can not damage the performance (being specially mechanical performance) of substrate such as glasses as Rockwell hardness and optical property as 1 to 100 μ m by the polymer film that solidifies the formation of photopolymerization and cured compositions.Thicker polymeric membrane will diminish the performance of base material.According to the present invention, the concentration of the photochromic compound in the polymer film can be up to 0.2 to 20% weight.Therefore, although described film thickness is very thin, also can give described substrate photochromic property.When the concentration of described photochromic compound was not less than 20% weight, the photochromic property with the laminate (polymer film) of infringement gained can be assembled or ooze out to described photochromic compound.On the contrary, when concentration during,, can not obtain enough photochromic properties even thickness reaches 100 μ m less than 0.2% weight.

Depend on the thickness of the polymer film that forms on the substrate curved surface, can suitably the concentration of photochromic compound be determined in above-mentioned scope (0.2 to 20% weight).This will hereinafter be described.

In the present invention, can use any known photochromic compound such as fulgimide compound, spiral shell piperazine compound and chromene compounds.These compounds are open in following document: for example patent disclosure of Japanese unexamined (Kokai) 2-28154,62-288830, WO94/22850 and WO96/14596.As compound, also can use those disclosed compound: 2001-114775 in the patent disclosure (Kokai) in following Japanese unexamined with excellent photochromic property, 2001-031670,2001-011067,2001-011066,2000-347346,2000-344762,2000-344761,2000-327676,2000-327675,2000-356347,2000-229976,2000-229975,2000-229974,2000-229973,2000-229972,2000-219687,2000-219686,2000-219685,11-322739,11-286484,11-279171,10-298176,09-218301,09-124645,08-295690,08-176139 and 08-157467.

In the photochromic compound of the invention described above, consider from light resistance, colour density and fade rates, also especially preferably use chromene compounds.Chromene compounds by following formula (18) expression has particularly advantageous photochromic property:

Wherein by the group of following formula (19) expression

For replacing or the aromatic hydrocarbyl of non-replacement or the unsaturated heterocycle base of replacement or non-replacement R ⁵¹, R ⁵²And R ⁵³The annelated heterocycles group that condenses for the alkynyl of aryl, halogen atom, aralkyl, hydroxyl, replacement or the non-replacement of amino, cyano group, replacement or the non-replacement of hydrogen atom, alkyl, alkoxyl, aralkoxy, amino, replacement, heterocyclic radical (described nitrogen-atoms and pyranoid ring bonding or close with ring key that following formula (19) is represented) or heterocyclic group and aromatic hydrocarbon ring or aromatic heterocycle independently of one another with replacement or non-replacement of nitrogen heteroatom, o is 0 to 6 integer, R ⁴⁹And R ⁵⁰Independently be heteroaryl, the alkyl of aryl, replacement or the non-replacement of replacement or non-replacement or the group of representing by following formula (20) or (21) separately,

R wherein ⁵⁴For replacing or the aryl of non-replacement or the heteroaryl of replacement or non-replacement R ⁵⁵Be hydrogen atom, alkyl or halogen atom, and p is 1 to 3 integer,

R wherein ⁵⁶For replacing or the aryl of non-replacement or the heteroaryl of replacement or non-replacement, p ' is 1 to 3 integer,

And R ⁴⁹And R ⁵⁰Can form aliphatic hydrocarbon ring or aromatic hydrocarbon ring together.

The aryl that replaces in following formula (20) and (21) or the heteroaryl R of replacement ⁴⁹And R ⁵⁰Substituting group can be radicals R ⁵¹And R ⁵²Illustrative those groups.

In the chromene compounds by following formula (18) expression, consider the preferred especially compound that uses by following formula (22) to (27) expression from light resistance, colour density and fade rates according to the present invention:

R wherein ⁵⁷And R ⁵⁸With R in the following formula (18) ⁴⁹And R ⁵⁰The illustration group identical, R ⁵⁹And R ⁶⁰With R in the following formula (18) ⁵³The illustration group identical, and q and q ' be respectively 1 to 2 integer,

R wherein ⁶¹And R ⁶²With R in the following formula (18) ⁴⁹And R ⁵⁰The illustration group identical, R ⁶³And R ⁶⁴With R in the following formula (18) ⁵³The illustration group identical, and L is any group that is expressed from the next:

Wherein P is oxygen atom or sulphur atom, R ⁵⁷For having the alkylidene of 1 to 6 carbon atom, s ', s " and s  be 1 to 4 integer, and r and r ' be 1 or 2 independently of one another,

R wherein ⁶⁶And R ⁶⁷With R in the following formula (18) ⁴⁹And R ⁵⁰The illustration group identical, R ⁶⁸, R ⁶⁹And R ⁷⁰With R in the following formula (18) ⁵³The illustration group identical, and v is 1 or 2,

R wherein ⁷¹And R ⁷²With R in the following formula (18) ⁴⁹And R ⁵⁰The illustration group identical, R ⁷³And R ⁷⁴With R in the following formula (18) ⁵³The illustration group identical, and w and w ' be 1 or 2 independently of one another,

R wherein ⁷⁵And R ⁷⁶With R in the following formula (18) ⁴⁹And R ⁵⁰The illustration group identical, R ⁷⁷, R ⁷⁸, R ⁷⁹And R ⁸⁰With R in the following formula (18) ⁵³The illustration group identical, and x and x ' be respectively 1 or 2,

R wherein ⁸¹And R ⁸²With R in the following formula (18) ⁴⁹And R ⁵⁰The illustration group identical, R ⁸³, R ⁸⁴And R ⁸⁵With R in the following formula (18) ⁵³The illustration group identical, described ring Q is aliphatic hydrocarbon ring and y, y ' and y " be respectively 1 or 2.

In these chromenes by following formula (22) to (27) expression of the present invention, most preferably use the chromene compounds of following structure:

In order to demonstrate required tone, above-mentioned photochromic compound suitably can be mixed use.

Consider that from the viewpoint that can dissolve to high-density the photochromic compound that mixes with photopolymerization of the present invention and hardening composition must be dissolved in the above-mentioned free yl polymerizating monomer (A) smoothly.But, different because solubility depends on the molecular structure of photochromic compound, so be difficult to from the required photochromic compound of the unique appointment of the viewpoint of solubility.The solubility of photochromic compound in free yl polymerizating monomer is generally about 1%.Therefore, in order to dissolve described photochromic compound more to high-density, need carry out some dissolution process.

According to the present invention, described photochromic compound can be dissolved in photopolymerization and the hardening composition (free yl polymerizating monomer) by the following method to high-density, for example photochromic compound is dissolved in to high-density in aprotic polar solvent such as the N-methyl pyrrolidone, the method of mixing subsequently with free yl polymerizating monomer, after perhaps photochromic compound being dissolved in low boiling point solvent such as carrene or THF to high-density, mix with polymerization single polymerization monomer immediately, then described low boiling point solvent is steamed the method for falling.

In order to obtain to contain the curable compositions of highdensity photochromic compound, the also available molecular compound of special chromene compounds and aromatic compounds component that contains is as photochromic compound.In this article, described molecular compound represent stable molecule wherein of the same race or not of the same race can predetermined ratio the direct compound of bonding mutually, the key that wherein forms between the component molecule of described molecular compound is looser, the initial configuration of component molecule and the character of key are not big to be changed, and described component molecule is more easily separated, reverts to their initial states.Usually, described molecular compound is the solid that a kind of composition is arranged according to predetermined ratio.When described molecular compound and the component molecular proportion that forms compound than the time, both demonstrate diverse physical property such as different fusing point, boiling point and solubility.

The above-mentioned molecular compound that the present invention is used does not have particular restriction, as long as it comprises special chromene compounds and aromatic compounds component ingredient, and described molecular compound can comprise several chromene compounds and several aromatic compounds.In addition, described component molecule can lump together by any formal bond, and to the ratio of component molecule in composition without limits.As for described proportion of composing, the combined optional of each chromene compounds and aromatic compounds is selected specific ratio.Yet in the molecular compound that can become photochromic compound (photochromic molecules compound), described ratio is generally chromene compounds: aromatic compounds=5: 1 to 1: 10 (mol ratio).

To the chromene of the component molecule (becoming photochromic compound) that forms various molecular compounds without any particular restriction, as long as it can form molecular compound with described aromatic compounds.Yet from being easy to form with aromatic compounds the viewpoint consideration of molecular compound, preferred described chromene compounds has phenyl at least one replacement or unsubstituted.In this chromene compounds, general owing between the phenyl of the replacement of chromene compounds and aromatic compounds, the interaction of pi-electron-pi-electron is arranged, so be easy to form described molecular compound.

In the present invention, in the chromene compounds of phenyl with at least one replacement or non-replacement, the preferred especially compound that uses by following formula (28) expression, because it can have favourable photochromic property:

R wherein ⁸⁶And R ⁸⁷Be to replace or the aryl of non-replacement or the aromatic heterocyclic group of replacement or non-replacement, and by the group of following formula (29) expression:

This group is many rings organic group that divalence condenses, and can have substituting group, and has and phenyl ring that the 2H-pyranoid ring of following formula (28) condenses.

Aromatic heterocyclic group R as substituted aryl in the formula (28) or non-replacement ⁸⁶And R ⁸⁷, example has phenyl, 1-or 2-naphthyl, 2-or 3-furyl, 2-or 3-thienyl and 2-or 3-pyrrolidinyl.

Described aryl or aromatic heterocyclic group R ⁸⁶And R ⁸⁷Not only can have a substituting group and also can have two or more substituting groups.Its kind is also had no particular limits.Preferred substituted is, for example the aryl of the amino of alkyl, alkoxyl, aralkoxy, replacement or non-replacement, cyano group, replacement or non-replacement, fluorine atom, chlorine atom, bromine atoms, iodine atom, aralkyl, trifluoromethyl, trifluoromethoxy, cyanogen methyl, aryl sulfonyl and alkyl sulphonyl.As the substituting group of illustrative substituted aryl above, the example that can enumerate for illustrative those substituting groups above but do not comprise the aryl of replacement.As the substituting group of illustrative substituted-amino above, except illustrative those substituting groups above, also comprise replacing or the having of non-replacement as heteroatomic nitrogen-atoms and by the heterocyclic group of nitrogen atom bonding to the phenyl ring, and the annelated heterocycles group that condenses with aromatic hydrocarbon ring or aromatic heterocycle.Described heterocycle can comprise except that with the nitrogen-atoms of phenyl ring bonding hetero atom, as oxygen atom, sulphur atom or nitrogen-atoms.

Consider the R in the preferred formula (28) from photochromic property ⁸⁶And R ⁸⁷For having the amino substituent phenyl of replacement or non-replacement.As the amino of described replacement or non-replacement, preferred exemplary group has amino; Alkyl amino is as methylamino, ethylamino, n-pro-pyl amino, isopropyl amino, normal-butyl amino and tert-butyl group amino; Dialkyl amido is as dimethylamino, diethylamino, di amino, diisopropylaminoethyl, di-n-butyl amino and di-t-butyl amino; Arylamino is as phenyl amino and naphthyl amino; And ammonia diaryl base, as diphenyl amino etc.Example as the amino of preferred replacement or non-replacement, also can enumerate replace or non-replacement have nitrogen heteroatom and by the heterocyclic group of nitrogen atom bonding to the phenyl ring, with aromatic hydrocarbon ring or the condensed hetero ring group that condenses with aromatic heterocycle, concrete example is for having 2 to 10 carbon atoms, preferred 2 to 6 carbon atoms and formed the heterocyclic group or the condensed hetero ring group of heterocyclic group, for example morpholino group, piperidino, pyrrolidinyl, piperazinyl (piperadino), N methyl piperazine base (piperadino) and indolinyl.

In following formula (28), be to have substituent fused polycycle organic group by the divalent group of formula (29) expression, and have and phenyl ring that the 2H-pyranoid ring of following formula (28) condenses.Though have no particular limits, consider that from the viewpoint that obtains excellent photochromic property the fused polycycle organic group is preferably the group by following formula (30), (31), (32) and (33) expression:

In following formula (30), R ⁸⁸And R ⁸⁹Independently of one another for hydrogen atom, alkyl, alkoxyl, aralkoxy, aralkyl, carboxyl, alkoxy carbonyl, can have substituent aryloxycarbonyl, aromatic alkoxy carbonyl, can have substituent amino, cyano group, nitro, can have substituent aryl, halogen atom, have nitrogen heteroatom and by nitrogen atom bonding to the ring of fused polycycle organic group heterocyclic group (can have substituting group) or the annelated heterocycles group that condenses with aromatic hydrocarbon ring or aromatic heterocycle.In addition, expression R ⁸⁸" aa " of the number of key is 0 to 3 integer, expression R ⁸⁹" ll " of the number of key is 0 to 2 integer, and as " aa " or " ll " when being not less than 2, a plurality of R ⁸⁸And R ⁸⁹Can be identical or different.At R ⁸⁸And R ⁸⁹In substituting group be preferably at least a group that is selected from alkyl, alkoxyl, aryl and halogen atom.

In following formula (31),, R ⁹⁰And R ⁹¹With the R in the following formula (30) ⁸⁸And R ⁸⁹Definition identical, the expression R ⁹⁰" mm " of the number of key is 0 to 2 integer, expression R ⁹¹" bb " of the number of key is 0 to 3 integer, and as " mm " or " bb " when being not less than 2, a plurality of R ⁸⁸Or R ⁸⁹Can be identical or different.

In following formula (32),, R ⁹²And R ⁹³With the R in the following formula (30) ⁸⁸And R ⁸⁹Definition identical, the expression R ⁹²And R ⁹³" cc " of the number of key and " dd " they are 0 to 3 integer, and as " cc " or " dd " when being not less than 2, a plurality of R ⁹²And R ⁹³Can be identical or different.

In following formula (33), by the ring of formula (34) expression,

Also can be aromatic hydrocarbon ring or unsaturated heterocycle, R ⁹⁴And R ⁹⁵With the R in the following formula (30) ⁸⁸And R ⁸⁹Definition identical, the expression R ⁹⁴And R ⁹⁵" ee " of the number of key and " ff " they are 0 to 3 integer, and as " ee " or " ff " when being not less than 2, a plurality of R ⁹⁴Or R ⁹⁵Can be identical or different.R ⁹⁶And R ⁹⁷Be amino, cyano group, nitro or the replacement of hydrogen atom, hydroxyl, alkyl, alkoxyl, aralkoxy, aralkyl, carboxyl, alkoxy carbonyl, aryloxycarbonyl, aromatic alkoxy carbonyl, replacement or non-replacement or the aryl of non-replacement independently of one another.In addition, R ⁹⁶And R ⁹⁷Also can combine the group that forms ketone group, can have substituent vinyl, comprise 1 or 2 oxygen atom and can have substituent heterocyclic group, can have substituent aliphatic hydrocarbon cyclic group or represent by following formula (35):

Wherein can be expressed from the next by-group that Y-represents:

Z wherein ¹And Z ²Be oxygen atom or sulphur atom independently of one another, R ⁹⁸, R ⁹⁹, R ¹⁰⁰And R ¹⁰¹Be alkylidene, and gg, hh, ii and jj are respectively 1 to 4 integer.

In the present invention, the suitable example that forms the chromene compounds (chromene compounds that just, has at least one replacement or non-substituted-phenyl) of above-mentioned molecular compound comprises following compound:

Aromatic compounds to other molecule of ingredient compound does not have particular restriction, as long as it can form molecular compound with above-mentioned chromene compounds.But, consider from the viewpoint that is easy to form described molecular compound, be 300 to 800 corresponding with the molecular weight of chromene compounds, preferred described aromatic compounds has and is specially 70 to 150 molecular weight.Because the size of aromatic compounds reduces and makes sterically hindered reducing, aromatic compounds can be positioned at above-mentioned pi-electron-pi-electron and is easy to take place interactional place like this.As this aromatic compounds, can use toluene, benzene, chlorobenzene, dichloro-benzenes, naphthalene, thiophene and pyrroles.

According to the present invention, by as can be known aforementioned, molecular compound as photochromic compound is the chromene compounds with at least one replacement or non-substituted-phenyl, and consider from photochromic property and the viewpoint that is easy to synthesize, be in particular by the chromene compounds with 300 to 800 molecular weight of following formula (28) expression and compound with aromatic compounds formation of 70 to 150 molecular weight.

(C) Photoepolymerizationinitiater initiater

In the present invention, mixed light polymerization initiator (C) is used for by polymerization and solidifies above-mentioned free yl polymerizating monomer (A) to form polymer film.As described Photoepolymerizationinitiater initiater, can use phosphorous Photoepolymerizationinitiater initiater.

With described the same, described phosphorous Photoepolymerizationinitiater initiater is except that the ultraviolet range, also do not divide under wavelength is not shorter than the activation-energy-ray effect of visible region of 400nm, thereby causes Raolical polymerizable.Regulating relative light intensity thus distributes.When radioactivation can ray relative intensity in the ultraviolet range when reducing, the polymerization and the coating of solidifying the polymerisable compound of the photochromic compound that contains high concentration equably, through its inside is not damaged described photochromic compound simultaneously.After cracking, because the photobleaching effect of himself, described phosphorous Photoepolymerizationinitiater initiater no longer absorbs visible light.Therefore, even, can cause described reaction equably continuously in the depth direction of coating.Aspect this, described phosphorous Photoepolymerizationinitiater initiater is very beneficial for solidifying equably through its inside of coating of polymerisable compound.

As phosphorous Photoepolymerizationinitiater initiater of the present invention, can use any compound known, consider from their excellent especially inside solidification performances, be in particular a kind of of monoacyl phosphine oxide or two acylphosphine oxides.

As described monoacyl phosphine oxide, can use compound by following formula (36) expression,

R wherein ¹⁰²Can be identical or different, be methyl, methoxyl group or chlorine atom, a ' is 2 or 3, and R ¹⁰³Be phenyl or methoxyl group,

For example 2,6-dimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,6-dichloro-benzoyl base diphenyl phosphine oxide or 2,6-dimethoxy benzoyl diphenyl phosphine oxide.

As described pair of acylphosphine oxide compound, can use compound by following formula (37) expression,

R wherein ¹⁰⁴Can be identical or different, be methyl, methoxyl group or chlorine atom, b ' is 2 or 3, and R ¹⁰⁵Can be 2,4, the 4-tri-methyl-amyl,

For example two (2,6-dimethoxy benzoyl)-2,4; 4-tri-methyl-amyl phosphine oxide, two (2, the 6-dimethylbenzoyl)-2,4; 4-tri-methyl-amyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide, two (2,6-dichloro-benzoyl base)-2; 4,4-tri-methyl-amyl phosphine oxide, two (2,4; the 6-trimethylbenzoyl)-phenyl phosphine oxide and two (2,4,6-trimethoxy benzoyl)-phenyl phosphine oxide.

In the present invention, above-mentioned phosphorous Photoepolymerizationinitiater initiater can use separately or two or more use together.In addition, because above-mentioned photochromic compound is to mix with high concentration, therefore, the above-mentioned free yl polymerizating monomer (A) of per 100 weight portions can be mixed with 0.01 to 10 weight portion, be specially 0.05 to 5 weight portion, and the phosphorous Photoepolymerizationinitiater initiater of 0.1 to 1 weight portion most preferably.

In the present invention, above-mentioned phosphorous Photoepolymerizationinitiater initiater also can use with the Photoepolymerizationinitiater initiater of any other type.Just, when using ultraviolet radiation, other Photoepolymerizationinitiater initiater can trigger described initiation reaction, therefore, even in the atmosphere that contains trace oxygen (tens to a hundreds of ppm), also can solidify the coating surface of described hardening composition effectively and not influenced by oxygen.Use phosphorous Photoepolymerizationinitiater initiater and other Photoepolymerizationinitiater initiater by uniting, can form one deck photochromic polymer film that all evenly solidify through its inside from the surface.This has enlarged concentration of oxygen scope in the atmosphere of polymerizing curable.Therefore, can regulate described atmosphere and be for example nitrogen replacement atmosphere of temperate condition comparatively, can finish polymerizing curable at short notice thus, can effectively prevent to be applied to on-chip curable compositions like this and drip, be very favourable for preventing that the photochromic polymer film thickness from disperseing and preventing wrinkle.This also helps improving the hardness of polymer film surface and the cohesive between enhancement polymer film and substrate or the hard conating.

As the Photoepolymerizationinitiater initiater except that above-mentioned phosphorous Photoepolymerizationinitiater initiater, the example that can enumerate is the compound by following general formula (38) or (39) expression:

R wherein ¹⁰⁶Be hydrogen atom, chlorine atom, methyl, ethyl, propyl group, methoxyl group, ethyoxyl, phenyl, carbomethoxy, methyl mercapto, morpholino base or 2-hydroxy ethoxy, R ¹⁰⁷For can having substituent phenyl or 1-hydroxyl-cyclohexyl,

R wherein ¹⁰⁸, R ¹⁰⁹And R ¹¹⁰Independently of one another for hydrogen atom, chlorine atom, methyl, ethyl, propyl group, butyl, methoxyl group, ethyoxyl, propoxyl group, butoxy, can have substituent phenyl, can have substituent benzyl, hydroxyl, morpholino base, N, N-dimethylamino, carbomethoxy or ethoxycarbonyl.

Instantiation by other Photoepolymerizationinitiater initiater of following formula (38) expression comprises benzophenone; methyl o-benzoyl yl benzoic acid ester; the o-benzoyl yl benzoic acid; 4-benzoyl-4 '-methyldiphenyl thioether; 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone; 1-hydroxyl-cyclohexyl-phenyl-ketone; 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; the 4-phenyl benzophenone; dihydroxy benaophenonel; 3; 3 '-dimethyl-4-methoxy benzophenone; benzoin; benzoin methylether; benzoin ethyl ether; benzoin iso-propylether; the benzoin isobutyl ether; 4-phenoxy group dichloroacetophenone; the 4-tert-butyl group-dichloroacetophenone; the 4-tert-butyl group-trichloroacetophenone; diethoxy acetophenone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone and 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, these compounds can use separately or two or more unite use.

Except compound by above-mentioned general formula (38) expression, also available phenol benzoate, acetophenone, 4,4 '-dichloroacetophenone, aminomethyl phenyl glyoxalic acid, thioxanthones, 2,4-dimethyl thioxanthones, 2-methyl thioxanthones, 2-clopenthixal ketone, diisopropyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 2-isopropyl thioxanthone, two (η ⁵-2,4-cyclopentadiene-1-yl)-two (2,6-two fluoro-3-(1H-pyrroles-1-yl)-phenyl) close titanium, 3,3, ' 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, camphorquinone, Dibenzosuberone, 2-EAQ, 4 '; 4 " benzene is for phenolphthalein, 9 between-diethyl, 10-phenanthrenequione and 1-phenyl-1,2-propanedione-2 (neighbour-ethoxy carbonyl) oxime is done other above-mentioned Photoepolymerizationinitiater initiater, can use separately or two or more unite use.

The combined amount that described Photoepolymerizationinitiater initiater except that phosphorous Photoepolymerizationinitiater initiater is general is above-mentioned free yl polymerizating monomer (A) 0.01 to 10 weight portion of per 100 weight portions, preferred 0.01 to 4 weight portion, more preferably 0.05 to 4 weight portion, most preferably 0.1 to 1 weight portion.The mixed proportion of phosphorous Photoepolymerizationinitiater initiater and other Photoepolymerizationinitiater initiater is different according to the concentration of photochromic compound in the polymerisable compound, can't indicate unique value.Yet, because phosphorous Photoepolymerizationinitiater initiater has than higher sensitivity of other Photoepolymerizationinitiater initiater and the activity of Geng Gao, therefore the ratio (weight ratio) of phosphorous Photoepolymerizationinitiater initiater/other Photoepolymerizationinitiater initiater be preferably 1/1 to 1/20 and, preferred 1/1 to 1/4.In addition, from preventing the ruined viewpoint of described photochromic compound, it is 5 to 50 weight portions that per 100 weight portion photochromic compounds (B) need to use the total amount of phosphorous Photoepolymerizationinitiater initiater and other Photoepolymerizationinitiater initiater, preferred 5 to 20 weight portions.

Other mix reagent

Except said components (A) to (C), also can under the condition of concentration in above-mentioned scope of for example photochromic compound (B), various suitable additives be added in photopolymerization of the present invention and the hardening composition.For example, in order to prevent the yellowing of described photochromic polymer film and light resistance, colour developing speed and fade rates, can add following additive such as surfactant, antioxidant, free radical scavenger, ultra-violet stabilizer, ultra-violet absorber, releasing agent, color preserving agent, antistatic additive, fluorescent dye, dyestuff, pigment, spices and plasticizer in order to improve crystallized ability, photochromic compound.

Described surfactant can be any nonionic, anionic or cationic surfactant.Yet, consider from the solubility described free yl polymerizating monomer (A), preferably use non-ionic surface active agent.Preferred nonionic comprises sorbitan fatty acid esters, fatty acid glyceride, the decaglycerin fatty acid ester, the propane diols pentaerythritol fatty ester, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, the polyoxyethylene fatty acid glyceride, cithrol, polyoxyethylene alkyl ether, polyoxyethylene phytosterol phytostanol, polyoxyethylene polyoxy-propylene, polyoxyethylene alkyl phenyl ether, Emulsifier EL-60, the castor oil of slaking, polyoxyethylene wool grease isocholesterol beeswax derivative, the polyoxyethylene alkyl amine fatty acid amide, polyoxyethylene alkylphenyl formaldehyde condensation products and strand polyoxyethylene alkyl ether.These surfactants can use separately or two or more unite use.The amount that adds surfactant in the free yl polymerizating monomer of per 100 weight portions (A) is preferably 0.1 to 20 weight portion.

As described antioxidant, free radical scavenger, ultra-violet stabilizer and ultra-violet absorber, can independent or multiple use hindered amine as light stabilizer, hindered phenol antioxidant, phenols free radical scavenger, sulphur-containing antioxidant, benzotriazole cpd and the benzophenone cpd of uniting together.The antioxidant, free radical scavenger, ultra-violet stabilizer and the ultra-violet absorber that preferably add 0.001 to 20 weight portion in per 100 weight portion bulk polymerization monomers.

Destroyed or in order to improve the light resistance of its curing materials (photochromic polymer film) in order to prevent described photochromic compound at the setting up period of polymerizable and hardening composition, preferably use the hindered amine as light stabilizer in the above-mentioned various additive.As preventing the ruined hindered amine as light stabilizer of photochromic compound especially effectively, can use two (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, by ASAHI DENKA Co., AdecastubLA-52, LA-62, LA-77 and the LA-82 of LTD. preparation.The addition of above-mentioned hindered amine as light stabilizer is: add 0.001 to 20 weight portion, preferred 0.1 to 10 weight portion, the most preferably hindered amine of 1 to 10 weight portion in the free yl polymerizating monomer of per 100 weight portions (A).

According to the present invention, different with above-mentioned Photoepolymerizationinitiater initiater, also can mix with the radical polymerization initiator (hot radical polymerization initiator) that produces free radical that is heated.Described thermal free radical initiator is preferably the initator that causes described radical polymerization under described substrate can not the temperature of thermal deformation, and exemplary example has diacyl peroxide such as dibenzoyl peroxide, chloro benzoyl peroxide, didecanoyl peroxide, lauroyl peroxide and acetyl peroxide; Peroxyester is as t-butyl peroxy-2 ethyl hexanoic acid ester, t-butyl peroxy two carbonic esters, cumyl peroxide neodecanoic acid ester and t-butyl peroxy benzoic ether; Peroxocarbonate is as diisopropyl peroxydicarbonate, two-2-ethylhexyl peroxide, two carbonic esters and two-sec-butoxy carbonic ester; And azo-compound, as 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (4-methyl pentane nitrile), 2,2 '-azo two (2-nitrile dimethyl) and 1,1 '-azo two (cyclohexane-1-formonitrile HCN), these compounds can use separately or two or more unite use.

The consumption of thermal free radical initiator depend on kind, the free yl polymerizating monomer of polymerizing condition, initator kind and composition, unite as the addition of the Photoepolymerizationinitiater initiater of initator and composition and different, and can not specify unique value.But per 100 weight portion free yl polymerizating monomers (A) generally use the hot radical polymerization initiator of 0.001 to 10 weight portion.

The preparation of photopolymerization and hardening composition

Method for above-mentioned photopolymerization of preparation and hardening composition does not have particular restriction.Just, the component of scheduled volume is weighed and mix to be easy to prepare photopolymerization and hardening composition.There is not particular restriction for the order that adds each component; Just, all components can add or only be pre-mixed free yl polymerizating monomer (A) simultaneously, adds and mix described photochromic compound (B) and other additive (for example adding before polymerization just) subsequently.

When described photopolymerization and hardening composition comprise described amines and at least a epoxy monomer, silyl group monomer and isocyanate-monomer, consider from storage stability, preferred described amines separates packing with the photopolymerizable composition that contains at least a epoxy monomer, silyl group monomer or isocyanate-monomer, in use these compounds is just mixed.In this case, other each component is fit to be assigned in above-mentioned two packings.

The preliminary treatment of substrate

In the present invention, above-mentioned photopolymerization and hardening composition are coated onto on the substrate curved surface to form coating, then this are coated with layers of polymer and curing, form the photochromic polymer film thus.Yet, before application, need anticipate described substrate and be coated with and install to described on-chip coating performance and cohesive to improve described photopolymerization and hardening composition.

For described preliminary treatment, can illustratively have by the chemical treatment of using alkaline aqueous solution or acidic aqueous solution, polishing, the plasma treatment of passing through to use atmospheric plasma and low pressure plasma, Corona discharge Treatment and UV ozone and handle by using polishing agent.Yet, consider from the bonding viewpoint between described substrate and the coating, preferably adopt atmospheric plasma to handle.In this article, described atmospheric plasma is handled and refer to the general plasma processing method of implementing under the pressure condition that is higher than the low pressure plasma processing.When under the pressure of about 1 holder, implementing the low pressure plasma processing, enforcement atmospheric plasma processing under the above-mentioned pressure can be higher than.

It is as air, nitrogen, oxygen, hydrogen, carbon dioxide, carbon monoxide, sulfur dioxide, argon gas, helium, neon, ammonia, chlorine, nitric oxide, nitrogen dioxide or freon such as CF that atmospheric plasma is handled ₄Or C ₂F ₆Atmosphere in implement.Yet,, preferably in air or nitrogen, carry out atmospheric plasma and handle from easy processing and cost consideration.In order to improve the cohesive of handling based on atmospheric plasma, wish that also the gas that uses has the 80%RH of being not more than at 24 ℃, particularly is not more than the relative humidity of 40%RH.

Though be not particularly limited, wish that the gas temperature in the atmospheric plasma processing is preferably-5 ℃ to 100 ℃, more preferably 5 ℃ to 60 ℃.

Though the method to radiating plasma in the atmospheric plasma processing is not particularly limited, the following method of preferred use:

(1) substrate is fixed on the spin coating device and when the described substrate of rotation, uses plasma resonance;

(2) described substrate is placed on fixing plasma resonance part below, and automatic or manual reaches the described substrate of move left and right back and forth with plasma treatment substrate surface equably; Perhaps

(3) fixing described substrate, automatic or manual reach move left and right plasma resonance part back and forth with described plasma treatment substrate surface equably.

In described atmospheric plasma is handled, as described in a slice metal or alloy can be inserted in as the shape sheet of iron, copper, aluminium or stainless steel (SUS) substrate and as described between the plasma resonance part.By using described shape sheet, substrate surface can be still less by electron discharge or heat damage during described atmospheric plasma is handled; Just, can implement effectively that described atmospheric plasma is handled and the surface of not destroying substrate.When using the substrate of plastic resin, effective especially with the method for thin slice.When using described shape sheet, also can obtain stronger cohesive and do not need as mentioned below to handle the step that back water or organic solvent clean at atmospheric plasma.

Implementing after atmospheric plasma handles, directly application photopolymerization and cured compositions.But, preferably clean to implement surface (solidified surface) that atmospheric plasma handles application photopolymerization and cured compositions more afterwards with solvent (cleaning solvent hereinafter referred to as).Because through cleaning, so can between described substrate surface and coating, obtain firm bonding.When atmospheric plasma is handled, not using above-mentioned metal net shaped thin slice, clean effective especially with cleaning solvent.

As described cleaning solvent, can make water; Alcohol is as methyl alcohol, ethanol, isopropyl alcohol, 1-butanols and 2-butanols; Ether is as oxolane, two  alkane and ether; Ester is as methyl acetate and ethyl acetate; With other organic solvent, as acetonitrile, acetone, hexane and toluene, these compounds can use separately or two or more mix use.Consider from improving bonding viewpoint, preferably make the mixed solvent of water or water and organic solvent.Specifically, owing to make water can very well reproduce bonding raising, in addition, waste water also is highly susceptible to handling, and therefore most preferably makes water.

When making the mixed solvent of water and organic solvent, preferred especially described organic solvent and water can evenly mix.For mixing water and organic solvent equably, preferred use can be at normal temperatures with water with arbitrarily than miscible water-miscible organic solvent as organic solvent, as methyl alcohol, ethanol or acetone.Also the mass ratio of preferred water/organic solvent is 100/0 to 1/99, more preferably 100/0 to 15/85.

As the organic solvent that is used to clean, can use the commercial any unpurified industrial solvent that gets.In addition, as water, can use urban water, ion exchange water, distilled water or pure water.

Kind or its mixing ratio that the temperature of cleaning solvent can be dependent on described substrate, water for cleaning, organic solvent are different and different, but preferably at-5 to 100 ℃, and most preferably 5 to 80 ℃.

Can clean with the substrate after the plasma treatment, for example by using above-mentioned cleaning solvent based on following well-known method:

(1) uses the substrate surface of having implemented the atmospheric plasma processing with the cloth wiping of an amount of cleaning solvent dipping;

(2) described cleaning solvent is poured in the container, the substrate of implementing the atmospheric plasma processing is immersed wherein, clean with ultrasonic wave; Perhaps

(3) will implement the substrate that atmospheric plasma handles and be placed on the spin coating device, an amount of cleaning solvent will be coated onto on the surface of (dripping to) plastic substrate, rotate described substrate then.

Although be not subjected to concrete restriction, consider no more than 10 times and of preferred wash number from production efficiency 1 to 5 time scope.In addition, two or more methods in the also available said method (1) to (3) are cleaned and have been implemented the substrate that atmospheric plasma is handled.When repeatedly cleaning, each cleaning solvent that cleans can be different.Kind, quantity and the temperature thereof that wash number depends on employed substrate, cleaning solvent be with described cleaning method and different, but generally between 3 seconds to 10 minutes.

In the present invention, can unite the above-mentioned various preprocess methods of use.Wherein, and the alkali treatment preprocess method of uniting use also effective especially to the cohesive that improves between substrate and the coating.Preferred preprocess method combination can be before or after plasma treatment or Corona discharge Treatment, perhaps used the method for aqueous slkali treatment substrate before or after using the polishing of polishing agent.But, in this article, preferably after plasma treatment, Corona discharge Treatment or polishing, implement alkali treatment.Described aqueous slkali is preferably sodium hydrate aqueous solution or potassium hydroxide aqueous solution.The concentration of hydroxide is preferably 5 to 30% weight.Can determine suitable treatment temperature according to the heat resisting temperature of substrate, but be preferably 20 to 60 ℃.Can implement the ultrasonic wave cleaning by described substrate being immersed in the aqueous slkali or when immersing described substrate in the aqueous slkali, thereby implement described processing.Processing time depends on treatment conditions and difference, but is preferably 1 minute to 1 hour, more preferably 5 to 15 minutes.Aqueous slkali also can be, for example the mixed solution of the mixed solution of water, various alcoholic solvents or the aqueous solution and alcoholic solution.The alcohol that uses is lower alcohol for example methyl alcohol, ethanol or isopropyl alcohol.Also can add a small amount of organic base such as 1-Methyl-2-Pyrrolidone as additive, its addition is per 100 weight portion aqueous slkalis, 1 to 10 weight portion.After with alkali treatment, available water (for example pure water, ion exchange water or distilled water) the described substrate of rinsing carries out drying then.

The application of photopolymerization and hardening composition and curing

After the described substrate of preliminary treatment, above-mentioned photopolymerization and hardening composition are coated onto on the described substrate curved surface to form coating.In this article, can carry out application, as spin coating, spraying, dip-coating or dipping spin coating by any known method.The amount of application, just, the coating layer thickness of photopolymerization and hardening composition can suitably be determined according to the thickness after solidifying, just, determine according to the desired thickness of photochromic polymer film.When needs increase the thickness of coating (for example, be not less than 10 μ m), the mixed proportion of suitably selective polymerization component such as free yl polymerizating monomer, and the viscosity (25 ℃) that can select photopolymerization and hardening composition 20 to 500cp, preferred 50 to 300cp, more preferably 60 to 200cp scope.When viscosity is low, evenly application photopolymerization and hardening composition, and also have the trend of dripping.For photopolymerization and the hardening composition that for example has above-mentioned viscosity by coating obtains the coating that thickness is not less than 10 μ m, preferably use spin-coating method.In this case, the coating layer thickness of substrate peripheral edge will increase.Therefore, as shown in Figure 1, preferably in spin coating operation by using scraper etc. to remove the liquid of excessive photopolymerization of substrate peripheral edge and hardening composition.By removing excess liq as mentioned above, the neighboring of cured film becomes more even, and except that the zone, neighboring, other regional thickness becomes more even, Δ W/W in above-mentioned zone _AvValue can be lower than 0.03 or below.Relevant is that the area in described zone can enlarge, and causes by Δ W/W therewith _AvThe uniform film thickness degree of expression is not more than 0.07 (in other words, Δ W/W _Av＞0.07 outer regions can be dwindled).

Fig. 1. illustrate when the described substrate 3 of rotation, the low side 2 of scraper 1 is contacted with liquid, thereby the liquid (photopolymerization and hardening composition) of substrate 3 ends is removed (though described substrate 3 has curved surface, Fig. 1 is in order to simplify the object of the plate-like of only having demonstrated) from the top of substrate 3.

Shape to employed scraper does not have special restriction, as long as it has and can remove after spin coating or reduce the photopolymerization that is positioned at substrate edge part and the alluvial liquid of hardening composition.But, required form as shown in Figure 2, Fig. 2 is the enlarged diagram of Fig. 1, and illustration low side 2 structures of scraper 1 of Fig. 1.Scraper 4 shown in Figure 2 (corresponding with scraper 1 shown in Figure 1) has a groove that is positioned at its low side, the shape of this groove is corresponding with the neighboring of substrate 8, and the shape and the substrate curve form on the limit 5 of groove match (Fig. 2 only is illustrated as the plane in order to simplify), and the shape on the limit 6 of groove and the edge shape of substrate 8 match.The formation of the groove of above-mentioned shape makes it remove alluvial liquid from substrate surface, thereby keeps predetermined width with the neighboring, and scrapes off the photopolymerization and the hardening composition of adhesion from substrate side, thereby improves the substrate profile after completion.The low side 7 of scraper 4 does not directly contact described substrate, but the structure that is fit to can allow scraper 4 keep intensity when rotary substrate.

Size to scraper 4 has no particular limits, and can use the scraper of any size, only otherwise the structure of device or operation are caused any problem to get final product.Preferred size can be: scraper 4 length are 1 to 30cm, and more preferably 3 to 20cm.Size to the groove part of scraper 4 also has no particular limits.Therefore, in this article, the length at edge 5 (1) has determined the scope of the alluvial liquid removed, and its length is generally 0.5 to 5mm, and preferred 0.8 to 3mm.Length (m) to edge 6 also is not particularly limited; Just, described length (m) can be equal to or less than the height (thickness) of substrate side.Specifically, described length (m) is preferably 1 to 15mm, and more preferably 1 to 10mm.Length (n) to the low side 7 of scraper 4 also is not particularly limited.But, consider the mechanical strength and the operability (when removing excessive coating solution) of scraper 4, described length (n) is preferably 0 to 55mm, is preferably 0 to 30mm.

Material to scraper is not particularly limited, can use plastic resin, as (methyl) acrylic resin, PETG, polypropylene, polyethylene, (foaming) polystyrene, (foaming) polyurethane resin, epoxy resin, PETG, polyvinyl chloride, Merlon, polytetrafluoroethylene (PTFE) and organic siliconresin; Metal is as stainless steel, aluminium, copper and iron; And rubber, as butadiene-styrene rubber, polybutadiene rubber, isoprene rubber, silicon rubber or acrylic rubber.Wherein, require the contact site between substrate and the scraper will contact the surface that the tight while does not scratch substrate again, therefore special hope is used has flexible plastic resin and rubber.

Can use described scraper as described below.Just, after being coated onto photopolymerization and cured compositions on the substrate surface, with the rotation of described substrate when finishing spin coating, this scraper can part contact with the neighboring of substrate surface (described substrate top be coated with photopolymerization and cured compositions), perhaps described scraper contacts with whole substrate surface to a suitable distance, for example on the substrate surface that has been coated with photopolymerization and cured compositions apart from neighboring 5mm.As for the disengaging time of described scraper and substrate, for photopolymerization and cured compositions are removed from the neighboring of substrate as far as possible, described scraper all keeps contacting with substrate to require to stop the rotation before just until substrate.In addition, although even figure of no use explanation when described scraper contacts with substrate side, owing to be spin coating, also can be removed the excessive photopolymerization and the hardening composition that stick to substrate side.Therefore, the profile that is improved after the described coating can solidified by methods such as photopolymerization.

Has the activation-energy-ray radiation that special relative intensity distributes, polymerization and the coating of solidifying photopolymerization and hardening composition by using through overregulating.Prevent simultaneously that in order to form even cured film described polymerization from being destroyed by oxygen, preferably the curing of being implemented by polymerization can be carried out in following atmosphere: this atmosphere has no more than 10, and 000ppm is particularly no more than 1, the molecule keto concentration of 000ppm.Can be by regulate the concentration of oxygen in the atmosphere with the method for inert gas replacement.Oxygen-free when described inert gas is inertia to free radical, but and low nitrogen of use cost or argon gas with high displacement efficiency.Require the oxygen concentration in the described atmosphere low as far as possible, make described polymerization undermined hardly.But, when the described atmosphere of displacement, can not get rid of oxygen fully, and molecular oxygen has the minute quantity infiltration inevitably.But, according to the present invention, use special Photoepolymerizationinitiater initiater can increase the acceptable concentration of oxygen, provide an advantage like this: promptly be easy to reach the concentration range of allowing by regulating oxygen concentration with inert gas replacement atmosphere.Just, can replace described atmosphere in a short period of time, this is for shortening the production time and preventing that described coating drippage from being very favorable.

As the activation-energy-ray that is used for initiated polymerization, can use ultraviolet ray or comprise the visible light of ultraviolet range.But, in order to form photochromic coating with uniform thickness, according to the present invention, need be with activation-energy-ray radiation with special relative intensity distribution map.Promptly be, adopt according to the present invention and to have activation-energy-ray radiation that following relative intensity distributes: be not shorter than 200nm but the relative intensity that is shorter than the wavelength component of 300nm is 0 to 5% so that photopolymerization and cured compositions are solidified, be not shorter than 300nm but the relative intensity that is shorter than the wavelength component of 400nm is 25 to 75%, be not shorter than 400nm but be 25 to 75% no longer than the relative intensity of the wavelength component of 500nm.In this article, regard the overall strength area of the activation-energy-ray in 200nm to 500nm zone as 100%, the relative intensity of activation-energy-ray is represented the ratio of the intensity area of the activation-energy-ray in the particular wavelength region.

200nm to 500nm wavelength region may is divided into the relative intensity that 3 wavelength region may are come the comparison activation-energy-ray, just be not shorter than 200nm still no longer than 300nm (regional A), but wavelength is not shorter than 300nm is not shorter than 400nm still no longer than 500nm (zone C) no longer than 400nm (area B) and wavelength.In this case, realize that from suppressing laminate to the destruction of described photochromic compound and gained the viewpoint of optical homogeneity considers that desired area A has low-intensity.From highly decomposing the described free yl polymerizating monomer consideration of described Photoepolymerizationinitiater initiater and height polymerization, wish that described area B has high strength.Consider from highly decomposing phosphorous Photoepolymerizationinitiater initiater, wish that also described zone C has moderate strength.Wherein particularly importantly described regional A has low-intensity.When the activation-energy-ray radiation that has big intensity with regional A when implementing polymerizing curable, to promote Photoepolymerizationinitiater initiater to decompose near coating surface, rate of polymerization between coating surface and the inside can be different thus, can form the uneven photochromic polymer film of optics like this.

Therefore, in the present invention, can regulate described activation-energy-ray and make it have following relative intensity distribution: regional A accounts for 0 to 5%, and area B accounts for 25 to 75%, preferably accounts for 50 to 75%, and zone C accounts for 25 to 75%, preferably accounts for 25 to 50%.

In addition, from even decomposition coating surface and inner Photoepolymerizationinitiater initiater and promote even polymerization to consider, also special favored area B particularly is not shorter than the zone that 360nm still is shorter than 400nm (area B ') and has big relative intensity.Specifically, the relative intensity of special desired area B ' is not less than 70% of the total relative intensity of area B, and the relative intensity of desired area B ' be not less than the whole zone of 200nm to 500nm relative intensity (100%) 35%.

In the present invention, the activation-energy-ray source that is used for initiated polymerization can be with the light source of electrode discharge or does not have the light source of electrode discharge, as long as it can give off the activation-energy-ray that is not shorter than 200nm.

Apply just alight pipe of voltage but have one with the light source of electrode discharge on electrode, its example comprises the ozone free high-pressure sodium lamp, contains the ozone high-pressure sodium lamp, high-pressure sodium lamp, sterilamp, krypton arc lamp, carbon arc lamp, xenon lamp, tungsten lamp, metal halide lamp, indium lamp and the thallium lamp of ultrahigh pressure mercury lamp, filling metal halide such as iron halide or gallium halide.But the light source of electrodeless discharge has one does not use electrode but control microwave energy alight pipe just, and its example comprises H lamp, Hplus lamp, D lamp, V lamp, M lamp and Q lamp.

In the present invention, when the relative intensity of the activation-energy-ray that produces when light source distributes and satisfies above-mentioned condition, can directly use light radiation so from light source.When the activation-energy-ray that produces when light source does not have above-mentioned relative intensity and distributes, can unite so and use two or more rays, perhaps use colour filter to adjust described ray, make it present above-mentioned relative intensity and distribute.

Usually, having following relative intensity from the activation-energy-ray of above-mentioned light emitted distributes: be not shorter than 200nm but no longer than the wavelength ingredients constitute 10 to 50% of 300nm, be not shorter than 300nm but no longer than the wavelength ingredients constitute 30 to 70% of 400nm, be not shorter than 400nm but no longer than the wavelength ingredients constitute 20 to 60% of 500nm.Therefore, can be by reducing the activation-energy-ray among the regional A, effectively control is in the relative intensity of the activation-energy-ray of above-mentioned zone.In order to reduce the activation-energy-ray among the regional A, the activation-energy-ray that described light source sends should be passed a colour filter.Can not be subjected to any any colour filter that restrictedly uses, be not more than 60% of the relative intensity that do not see through before the colour filter as long as the material of preparation colour filter can be reduced to the relative intensity of the activation-energy-ray that is shorter than certain wavelength that sends from light source, preferably be not more than 30%.For example, can use ultraviolet cutoff colour filter, hard soda-lime glass or transparent glass material or the resin that applies with the ultraviolet light cut film.As required, described colour filter surface or two surfaces can be the frosted attitude.For example, energy for the activation-energy-ray that reduces to be shorter than 300nm or to be shorter than 360nm can use filter glass UV-30 (the ultraviolet transmission wavelength-limited of transmission 300nm wavelength) or filter glass UV-36 (the ultraviolet transmission wavelength-limited of transmission 630nm wavelength).In this article, the transmission wavelength-limited is a speech by JIS B7113 regulation, and the meaning is that to be positioned at the light transmission factor be that 72% wavelength A and light transmission factor are the wavelength of the centre of 5% wavelength B.

Usually, the light source of photopolymerization use can be selected by the activation wavelength of considering employed polymerization agent.But, in the present invention, from the relative intensity of the activation-energy-ray that reduces above-mentioned zone A with use the colour filter that is easy to get to regulate the viewpoint that described Wavelength distribution meets above-mentioned scope easily and consider, the preferred light source that electrode is arranged that uses is as metal halide lamp or ozone free high-pressure sodium lamp or electrodeless lamp such as D lamp, V lamp, M lamp or Q lamp.Consider from the relative intensity of the activation-energy-ray that reduces regional A and the viewpoint of relative intensity that increases the activation-energy-ray of area B (but principal spectrum of light source is not shorter than 300nm is shorter than 400nm), especially preferably use metal halide lamp, ozone free high-pressure sodium lamp or D lamp.

In order to obtain the uniform laminate of optics according to the present invention, the relative intensity that needs the control activation-energy-ray is in preset range and prevent that the substrate surface temperature from raising during handling solidifying.Just, control substrate surface temperature is not higher than 100 ℃, particularly is not higher than 80 ℃.Be not higher than predetermined value by the temperature that suppresses substrate surface with described activation-energy-ray radiation simultaneously, can suppress the distortion of described substrate, thus reduce form before the polymer film and afterwards the curvature of substrate curved surface intensity of variation and prevent that optical property from descending.When use has the substrate of low Tg,, perhaps when the thin substrate of the center of curvature thickness that uses curved surface very little (for example, being not more than 2mm), can obtain special obvious effects as polyurethane resin or polymethacrylate resin.

For the temperature with substrate surface remains in the above-mentioned scope, must effectively remove the heat ray that sends by light source.For this purpose, can use and be contained in conbination cassing around the light source and allow pure water flow into as the method in the chucks such as water cooling chuck system, with Pyrex glass (registration mark, forming the multiple layer metal thin layer by gasification obtains, can allow infrared ray see through) be trapped among around the light source, and use as the method for substrate as described in the uv reflectance radiation such as cold reflector system and use the method for heat ray by colour filter.In above-mentioned system, consider from easy viewpoint, preferably use heat ray to end the colour filter system.

Described heat ray is represented to have by absorption or reflect visible light and infrared ray to suppress the optics colour filter of heat ray transmission function by colour filter.In the present invention, described heat ray is placed between thermal source and the described substrate by colour filter, thus can be easily and when suppressing to solidify effectively the substrate surface temperature raise.By colour filter, can use that the average light transmission factor is not more than 60% in the wavelength region may of the wavelength region may of 0.8 to 1 μ m or 3 to 5 μ m as heat ray, preferably be not more than 30% colour filter.

As the material of heat ray, can use any known material without restriction, as inorganic material, organic material or inorganic/organic composite material by colour filter.Wherein, consider, especially preferably use inorganic material from hear resistance.As the example of inorganic material, that can mention has cold colour filter, aluminium reflective mirror, quartz plate and coloured glass.In this article, described cold colour filter represents for example to plate from the teeth outwards by vacuum evaporation the quartz glass plate of multiple layer metal oxide, described aluminium reflective mirror represents to have the mirror that the aluminum by high brightness of the minute surface that demonstrates high reflection factor is equipped with, coloured glass is represented colored transparent glass, the phosphate glass or the soda-lime glass that comprise iron content also contain iron, nickel, cobalt or the selenium of trace.Can use a kind of or unite and use multiple heat ray by colour filter.In the colour filter, especially preferably use coloured glass at above-mentioned heat ray, because the temperature that it can suppress substrate such as lens surface efficiently raises and the activation-energy-ray that wavelength is longer than 300nm is had high transmission factor.

Can end efficient, select heat ray to end the thickness of colour filter in the transmission factor of ultraviolet ray and visible region by considering heat ray, but be generally 0.01mm to 10mm, preferred 0.1 to 5mm.

In the present invention, the time of radioactivation energy ray can be selected according to the wavelength of light source and the shape of intensity and lamp, but is generally 1 second to 10 minutes, is preferably 10 seconds to 5 minutes.Though be not particularly limited, preferred radiation intensity, just activation-energy-ray arrives described on-chip intensity and is not more than 30mW/cm ², especially the light intensity at wavelength 315nm place is not more than 15mW/cm ², the light intensity at wavelength 365nm place is 30 to 90mW/cm ², particularly 30 to 70mW/cm ², the light intensity at wavelength 405nm place is 50 to 200mW/cm ², particularly 70 to 150mW/cm ²Radiation length can be selected according to radiation intensity and radiated time, but is generally 10cm to 80cm.When increase with light source apart from the time, described substrate can less be accepted the heat sent by described light source.Therefore, wish to use a kind of light source, use fan to be the heat radiation of light source system simultaneously, and realize radiation at 40 to 80cm radiation length with big as far as possible radiation intensity.During this external radiation, also described substrate can be fixed or described substrate is placed on the conveyer belt radiation one or many.

By with aforesaid activation-energy-ray radiation, can be coated with layers of polymer and curing with what form on the substrate curved surface, thereby form polymer film.In this article, described photopolymerization and cure polymer and described thermal polymerization or above-mentioned epoxy monomer, silyl group monomer or isocyanate-monomer and as the component (passing through condensation curing) of amines when mixing, as required, hot polymerization is incompatible to be finished by implementing after the available activation-energy-ray radiation of described curing.When thermal polymerization, preferably under 110 to 130 ℃ temperature, heat described substrate, particularly heated 30 minutes to 3 hours down at 110 to 120 ℃, more preferably heating 1 to 2 hour under can the condition of whole evenly heating (this heating can the batch (-type) baking oven carries out by for example using) with described substrate, because between substrate and polymer film, formed thermal bonding and chemical bonding, so can obtain good bonding.When carrying out photocuring with the activation-energy-ray radiation, described near surface not only is locally heated, and because polymerization shrinkage has produced huge stress.Therefore, in order to prevent described substrate distortion, described substrate must be remained in the temperature that is not higher than 100 ℃.But described thermal polymerization does not have the problems referred to above, even no problem above heated substrate under 100 ℃ the temperature yet.

Laminate

Therefore, according to the present invention, can obtain to be laminated to the laminate on the substrate curved surface with photochromic polymer film.

This laminate has excellent optical property, and diopter and the dioptric difference of the curing face (surface of polymer film) of laminate of substrate curved surface before forming the photochromic polymer film simultaneously is very little.Specifically, the difference of the refraction at spherical surface ability of above-mentioned curved surface can be defined as less than ± 0.5 diopter, preferably less than ± 0.1 diopter, be more preferably less than ± 0.3 diopter.Just, laminate of the present invention can highly keep it to have optical property under the undermined substrate (and lens) hardly, and the polymer film that forms on described substrate can keep homogeneous thickness and whole polymer film can keep the very high uniformity, and before polymer film forms and do not cause curature variation afterwards basically.Just, except being divided by the peripheral edge portion on lamination surface, the polymer film in whole (center) zone all is uniform.Maximum film thickness (W _Max) or minimum thickness (W _Min) and average film thickness (W _Av) between poor (Δ W=W _Max-W _AvOr W _Av-W _Min) be not more than 7% (Δ W/W _Av≤ 0.07), preferably is not more than 5% (Δ W/W _Av≤ 0.05), and most preferably is not more than 3% (Δ W/W _Av≤ 0.03).Specifically, even form the homogeneous polymer film on can the film of very little at the thickness at curvature of curved surface center (just being not more than 2mm).

In this article, the neighboring of removing (center) region representation of polymer film peripheral edge portion office and the polymer film interior zone (part) of preset distance of being separated by, and area that should zone (part) accounts for 70% of laminate total surface area at least, and preferably at least 85%.For example, general as glasses when described substrate is the circular of diameter 60mm to 80mm or during for sub-circular, described (center) region representation is apart from neighboring 6.5 to 4.9mm, particularly 3.1 to 2.3mm part.Above-mentioned maximum film thickness (W _Max), minimum thickness (W _Min) and average film thickness (W _Av) be the one-tenth-value thickness 1/10 of measuring at least five differences (position).

Thickness at substrate peripheral edge polymer film partly can increase above 0.07 usually (by above-mentioned relation formula Δ W/W _AvExpression), the part that exceeds the neighboring is all the more so.But in glasses, generally when the machining lens make its shape that meets picture frame, described outer peripheral portion is removed, therefore no problem fully in use.

In the laminate of the present invention by method for preparing, the photochromic polymer film that forms on the substrate curved surface is extremely thin, as 1 to 100 μ m.Therefore, the polymer film of formation can not destroy the performance (particularly mechanical performance such as Rockwell hardness and optical property) of substrate.In addition, described photochromic polymer film contains the photochromic compound up to 0.2 to 20% weight, therefore, although its very thin thickness also is enough to give the substrate photochromic property.

When the concentration of the photochromic compound in the polymer film increases when surpassing 20% weight, described photochromic compound is tending towards assembling or oozing out, and obtains the laminate that shows that photochromic property is impaired.On the contrary, when described concentration during,, can not obtain enough photochromic properties even described thickness increases to 100 μ m less than 0.2% weight.

The preferred concentration of the photochromic compound in the polymer film is relevant with thickness, and preferably considers photochromic property (colour density, light resistance and priming color) when regulating in above-mentioned scope.For example, compare with thickness too hour when concentration, colour density can reduce.On the contrary, compare with thickness when too high when concentration, priming color is tending towards thickening.Therefore, when using photochromic lens, the concentration of wishing thickness and photochromic compound is 20 to 50 μ m and 2 to 7% weight, is preferably 30 to 50 μ m and 3 to 7% weight.

Laminate with photochromic property of the present invention can be used as the optical goods of various application, the glass pane of for example transparent film, glasses, house and automobile etc.

When laminate of the present invention as glasses (just with glasses as substrate and form described photochromic polymer film in its surface) time, require the refractive index of polymer film to be approximately equal to the refractive index of glasses.Regulate refractive index by regulating the mixed proportion of free yl polymerizating monomer (A) in photopolymerization and hardening composition, and generally pass through this adjusting, the material (polymer film) after it solidifies can demonstrate about 1.48 to about 1.75 refractive index.

When described photopolymerization and hardening composition and above-mentioned silyl group monomer and/or isocyanate-monomer and amines were mixed, the polymer film that forms on glasses (specifically the referring to Plastic eyeglasses) surface can demonstrate with the glasses that constitute substrate very high bondability.

Laminate of the present invention with photochromic polymer film can directly be used as photochromic optical material.But more preferably use hard material coated polymer film.After the hard material coating, described photochromic optical material can demonstrate the scratch resistance performance of raising.

Can use any hard coating material without restriction, for example mainly comprise the silane coupler of colloidal sol of the oxide of silicon, zirconium, antimony or aluminium, perhaps use the hard coating material that consists predominantly of organic polymeric material.

The surface that applies with hard material also can apply layer of metal oxide such as SiO again by vacuum evaporation ₂, TiO ₂, ZrO ₂Film or stand antireflection and handle by applying one deck organic polymer material film in its surface, and stand antistatic and handle and after-treatment.

Embodiment

By example the present invention is described now.

(1) photochromic compound

PC1: with the compound of 1: 1 following compound (A) of mol ratio and toluene preparation.

The preparation of PC1

In heating, the green crystal of above-claimed cpd (A) is dissolved in the toluene of 10 times of volumes, at room temperature stirred recrystallization and filtering 24 hours.The material of gained is no longer reduced until weight at 80 ℃ of following drying under reduced pressure, obtained the molecular compound of yellow powder shape thus.The fusing point of the molecular compound PC1 that mensuration obtains is 162 ℃, and the fusing point of described compound (A) is 273 ℃, can determine to have formed described molecular compound by contrast like this.With the mol ratio of toluene by ¹H-NMR measures.

PC2: with the compound of 1: 1 following compound (A) of mol ratio and toluene preparation.

The preparation of PC2

In heating, the red crystals of above-claimed cpd (B) is dissolved in the toluene of 10 times of volumes, at room temperature stirred recrystallization and filtering 24 hours.The material of gained is no longer reduced until weight at 80 ℃ of following drying under reduced pressure, obtained the molecular compound of yellow powder shape thus.The fusing point of the molecular compound PC2 that mensuration obtains is 113 ℃, and the fusing point of described compound (B) is 185 ℃, can determine to have formed described molecular compound by contrast like this.With the mol ratio of toluene by ¹H-NMR measures.

(2) free yl polymerizating monomer

M1: mean molecule quantity be 776 2, two (the 4-methacryloxy polyethylene glycol phenyl) propane of 2-

M2: polyethyleneglycol diacrylate (mean molecule quantity is 532)

M3: trimethylol-propane trimethacrylate

M4: polyester oligomer six acrylate (EB-1830 is by DAICEL UCB COMPANYLTD. preparation)

M5:GMA: GMA

M6:DPEHA: dipentaerythritol acrylate

M7: urethane oligomer six acrylate (U-6HA is by Shin-Nakamura Kagaku Co. preparation)

M8: γ-methacryloxypropyl trimethoxy silane

(3) Photoepolymerizationinitiater initiater

IN1:CGI184:1-hydroxy-cyclohexyl phenyl ketone

IN2: two (2,6-trimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide

(4) amines.

The NMDEA:N-methyl diethanolamine

DMEMA: methacrylic acid N, N-dimethylaminoethyl ester

(5) stabilizing agent.

LS765: two (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate

(6) optical material.

CR39 (allyl resin lens, refractive index=1.50)

MR (sulfo-polyurethane resin lens, refractive index=1.60)

Embodiment 1

Above-mentioned free yl polymerizating monomer is mixed according to ratio shown in the table 1, thereby obtain polymerisable compound.

In the mixture of the above-mentioned free yl polymerizating monomer of 100 weight portions, add photochromic compound PC1, the PC2 of 1.5 weight portions, the PC3 of 0.3 weight portion, PC4 and the Photoepolymerizationinitiater initiater IN1 of 0.375 weight portion and the IN2 of 0.125 weight portion of 0.3 weight portion of 2.7 weight portions.Also can add LS765 (5 weight portion) as light stabilizer and NMDEA (3 weight portion) as other additive, and described mixture stirred fully.Can under 25 ℃, measure the dynamic viscosities of mixed solution with the Cannon-Fenske viscosimeter according to the method for JIS K2283.By using the proportion of dynamic viscosity that obtains and the sample of measuring in advance, can be 110cp according to following formula working sample viscosity:

Viscosity (cP)=dynamic viscosity (cSt) * proportion (g/cm ³).

Then, use the spin coater 1H-DX2 of MIKASA Co. preparation will about 2g to revolve-be coated onto center thickness by the mixed solution that said method obtains and be 7mm as 1mm, end thickness, diameter is on the surface of plastic lens MR of 75mm.In spin coating operating period, keep shape scraper as shown in Figure 2 to contact, to remove the excessive coating solution that amasss in the neighboring of plastic lens part with described lens by the polyurethane resin preparation.Use the scraper of Fig. 2, it has the limit 5 that long l is 3mm, and long m is the limit 6 of 5mm and the lower portion 7 that long n is 10mm.

After spin coating, described film is solidified by photopolymerization under condition as shown in Figure 2.Wavelength 405nm place intensity is 80mW/cm during just, with the arrival lens surface ³Light come the coated lens surface of radiation, electrodeless D lamp (distance between described substrates of lenses and the light source is 60cm) below wherein in blanket of nitrogen (oxygen concentration is 800ppm), having used, and used hard soda-lime glass to do the ultraviolet cutoff colour filter to solidify described film.

Electrodeless D vacuum lamp

Model is by the F300SQ-6 of Fusion UV Systems Japan Co. preparation.

Light source is in 200 to 500nm intensity distributions:

200 to 300nm:16%

300 to 400nm:56%

400 to 500nm:28%

Behind soda-lime glass really up to the mark, light source is in 200 to 500nm intensity distributions:

200 to 300nm:2%

300 to 400nm:64%

400 to 500nm:34%

After solidifying, by using the temperature of thermocouple measurement lens surface, the highest temperature is 80 ℃.By heat treatment in 110 ℃ baking oven 1 hour, the lens of photochromic polymer film that can obtain on it lamination.The plastic lens that uses can be the surface and has stood the atmospheric plasma that the plasma radiation device (ST-7000) by Keyence Co preparation carries out (plasma that is formed by nitrogen) and handle, and uses 50 ℃ of its surperficial lens of hot water cleaning the improvement.

Thus obtained lens with photochromic polymer film can be estimated by method as described below.

(1) colour density (Abs.): with after the light radiation 120 seconds, the absorption { ε (120) } of maximum absorption wave strong point during with light radiation of no use curing materials be decided to be colour density in the difference { ε (120)-ε (0) } of the absorption { ε (0) } at above-mentioned wavelength place.This value is high more, and described photochromic property is excellent more.

(2) fade rates (min.): after with light radiation 120 seconds, stop radiation, and measure curing materials is reduced to a half of above-mentioned difference { ε (120)-ε (0) } in the absorption of maximum absorption wave strong point time { t1/2 (min) }.This time is short more, and described photochromic property is excellent more.

(3) show tone:, determine the tone of demonstration with eyes out of doors with the sunlight colour developing.

(4) durability: the accelerated aging test below implementing is to estimate the durability of exposure colour developing.Just, the lens with photochromic coating that obtained by said method can be stood 200 hours accelerated aging tests, carry out this test by the aging machine of xenon that uses Suga Shikenki Co. preparation.Then, the colour density (A200) after colour density (A0) before the determination test and the test and will (A200/A0) * 100} is decided to be the residual rate (%) as the index of the durability that develops the color.Described residual rate is high more, and the light resistance of colour developing back color is good more.

(5) yellowness (YI): can use by the colour difference meter (SM-4) of Suga Shikenki Co. preparation and measure the colour developing yellowness of lens specimen before.Described YI value is big more, and the yellowing degree is strong more.

(6) outward appearance: can be by the following relevant item outward appearance of lens of photochromic polymer film of having estimated lamination on it.The check result of opening this project of circle expression is all qualified.In table 3, listed the defective that exists.

1. the defective that is caused by thermal deformation: watch lens surface attentively when fluorescent lamp is contacted with lens, the reverberation of fluorescent lamp is out of shape.

2. defective curing: most monomer does not have polymerization, and during with acetone wiping lens surface, shade can occur on the lens.

3. defective shape: the shape on film surface is obviously undesired.

(7) cohesive: can by with the icking tool with sharp edges thereon lamination the limit of lens surface portrayal coating of photochromic polymer film, form the grid of 100 1mm * 1mm.Then, peel off situation about peeling off with eye examination coating (coating) with the commercial adhesive tape that gets (Cellotape, registration mark) is sticking thereon and fast.Two circle expressions do not have grid to be stripped from, and open the circle expression and are no less than 90 grids and keep not being stripped from, and triangle represents that 50 to 90 grids keep not being stripped from, and * expression is no less than 50 grids and is stripped from.

(8) thickness of photochromic polymer film: by using the thickness of measuring film by the film analyzer of Filmetrics Co. preparation.In order to find out W _AvWith Δ W/W _AvMeasure thickness along a line that passes substrate center, be divided into 5 equal portions with the center with apart from the distance between the inside of neighboring 5mm simultaneously, just measure 6 points altogether, comprise the center, apart from point of the inside of neighboring 5mm with 4 points of five equilibrium between above-mentioned 2.Table 3 illustrated the result.

In table 3, Δ W/W _AvExpression is based on W _MaxAnd W _Min{ (the Δ W/W of value between the two (whichsoever bigger) _Av) * 100}%.When containing the wrinkle that to determine by eyes in the described photochromic compound layer or when described photochromic compound is not fully solidified, can not using above-mentioned Instrument measuring.

(9) optical property: use by Automation ﹠amp; The reflection-type curvature analyzer FOCOVISION SR-1 of Robotics Co. preparation measures lens before lamination photochromic polymer film and the difference of the refraction at spherical surface ability after the lamination.Dicyclo represents that difference is less than ± 0.03 diopter, open circle expression difference to be not less than ± 0.03 diopter but less than ± 0.1 diopter, triangle table differential value is not less than ± 0.1 diopter but less than ± 0.5 diopter, and * the expression difference is not less than ± 0.5 diopter.Described difference is more little, and the optical property of lens before and after lamination photochromic polymer film changes more little.When containing the wrinkle that to determine by eyes in the described photochromic polymer layer or when described photochromic compound is not fully solidified, can not using above-mentioned Instrument measuring.

Embodiment 2 to 6

Have the lens specimen of photochromic polymer film by the method preparation the same, but mix the hereinafter polymerisable monomer shown in the table 1 with embodiment 1, and change embodiment 1 radiation condition as shown in table 2.Table 3 has provided assess performance.Listed the result in the table 3.

Comparative examples 1 to 3

Have the lens specimen of photochromic polymer film by the method preparation the same, but mix the hereinafter polymerisable monomer shown in the table 1 with embodiment 1, and the radiation condition of change embodiment 1 as shown in table 2.Assess performance is as shown in table 3.Listed the result in the table 3.

As shown in table 3, except optical property be *, described properties of sample conforms to laminated material of the present invention.When the embodiment in the table 31 was compared with comparative examples, the lens surface temperature during with the light radiation lens in the comparative examples 1 became too high, developed into defective owing to thermal deformation like this and can cause described photochromic polymer film and the distortion of described substrate.In not using the comparative examples of the present invention 2 of ultraviolet cutoff colour filter, only promoted the polymerization on described surface, and the rate of polymerization of described inside has fallen behind.Therefore, on described surface, formed wrinkle.In the comparative examples 3 of not using phosphorous-Photoepolymerizationinitiater initiater, only there is the very polymerization of low degree on the surface, and inside does not still have polymerization, and this can cause defective curing.

Table 1

Numbering	Free yl polymerizating monomer (weight portion)	Photochromic compound (part)	Amines (part)	Photoepolymerizationinitiater initiater (part)	Stabilizing agent (part)
Numbering	Free yl polymerizating monomer (weight portion)	Photochromic compound (part)	Amines (part)	Photoepolymerizationinitiater initiater (part)	Stabilizing agent (part)	Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative examples 2 comparative examples 3	M1/M2/M3/M4/M5/M8 43/15/15/10/10/7 M1/M2/M3/M4/M5/M8 43/15/15/10/10/7 M1/M2/M5/M6/M7 40/25/10/10/15 M23/M5 50/50 M1/M2/M3/M4/M5/M8 43/15/15/10/10/7 M1/M2/M3/M4/M5/M8 43/15/15/10/10/7 M1/M2/M3/M4/M5/M8 43/15/15/10/10/7 M1/M2/M3/M4/M5/M8 43/15/15/10/10/7 M1/M2/M3/M4/M5/M8 43/15/15/10/10/7	PC1 3 PC1/PC2/PC3/PC4 2.7/1.5/0.3/0.3 PC1/PC2/PC3/PC4 2.7/1.5/0.3/0.3 PC2 10 PC1 3 PC1 3 PC1 3 PC1 3 PC1 3	NMDEA 3 NMDEA 3 NMDEA 3 - NMDEA 3 NMDEA 3 NMDEA 3 NMDEA 3 NMDEA 3	IN1/IN2 0.375/0.125 IN1/IN2 0.375/0.125 IN1/IN2 0.375/0.125 IN1/IN2 0.375/0.125 IN2 0.4 IN2 3 IN1/IN2 0.375/0.125 IN1/IN2 0.375/0.125 IN1 0.4	LS765 5 LS765 5 LS765 5 LS765 5 LS765 5 LS765 5 LS765 5 LS765 5 LS765 5

Table 2

Numbering	The lens material Material	Light source	Radiation intensity (the mW/cm of the light of the 405nm of lens surface ²)	Radiated time (minute)	Ultraviolet light ends Colour filter	Heat ray cuts End Colour filter	Photocuring rear lens table The temperature of face (℃)
Numbering	The lens material Material	Light source		Radiated time (minute)	Ultraviolet light ends Colour filter	Heat ray cuts End Colour filter	Photocuring rear lens table The temperature of face (℃)	Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative examples 2 comparative examples 3	MR MR CR39 MR MR MR MR MR MR	Electrodeless D lamp is electrodeless, and the electrodeless D lamp of the electrodeless D lamp of D lamp metal halide hangs down the electrodeless D lamp of the electrodeless D lamp of the electrodeless D lamp of pzpne high-pressure sodium lamp	80 80 80 50 80 80 150 80 80	2 2 4 8 2 2 1 2 2	The hard hard soda-lime glass of the hard soda-lime glass of the hard soda-lime glass of the hard soda-lime glass of the hard soda-lime glass of the hard soda-lime glass of soda-lime glass-hard soda-lime glass	--cold colour filter------	80 80 70 80 80 80 130 80 80

Table 3

Numbering	Colour density (Abs)	Fade rates (minute)	Tone	Durability (％)	Yellowness Y1	Outward appearance	Bonding The property	Thickness W _av (μm)	ΔW/W _av (％)	Optics Performance
Numbering	Colour density (Abs)	Fade rates (minute)	Tone	Durability (％)	Yellowness Y1	Outward appearance	Bonding The property	Thickness W _av (μm)	ΔW/W _av (％)	Optics Performance	Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative examples 2 comparative examples 3	0.9 0.77 0.80 1.02 0.67 0.50 0.9 A A	1.1 1.2 1.1 1.9 1.6 1.7 1.3 A A	Blue grey grey is orange blue blue	55 45 50 30 48 10 48 A A	14 13 13 23 14 30 14 A A	The defective shape of 000000 thermal deformations, the bad curing of surperficial crumple	◎ ◎ ◎ ○ ○ ○ △ × ×	40 42 45 19 41 42 38 A A	2.5 2.4 2.9 2.6 1.9 2.0 2.1 A A	◎ ◎ ◎ ○ ○ ○ × × ×

A: energy measurement not

Method of the present invention can have the substrate of curved surface (such as common available glasses) form even and thin, contain the high concentration photochromic compound and have the film of uniform thickness, and in the very good mechanical properties and optical property that keep substrate, give its photochromic property.

In addition, the laminate of the present invention that obtains by said method not only demonstrates excellent photochromic property but also compares with conventional photochromatic layer, and laminate of the present invention has that thickness is littler, the more equal higher photochromic coating of even performance uniformity of thickness. In addition, preferred photopolymerization and the hardening composition that uses can be without mould among the preparation method of the present invention, be applied on the substrate surface, in gas atmosphere (just in Development System), solidify in the short time, even even but in containing the air of a small amount of oxygen or when containing the photochromic compound of the light that the absorbing polymer of high concentration uses, by suitably regulating the Wavelength distribution of radiant light, also can be allowed to condition in the short time and solidify.

Claims

1. the method for a prepared layer compressing tablet, described method comprises:

The substrate of preparation band curved surface;

Described photopolymerization of activation-energy-ray radiation curing and cured compositions that apparatus has following relative intensity to distribute: be not shorter than 400nm but be 25 to 75% no longer than the relative intensity of the wavelength component of 500nm, but the relative intensity that is not shorter than 300nm is shorter than the wavelength component of 400nm is 25 to 75%, but the relative intensity that is not shorter than 200nm is shorter than the wavelength component of 300nm is 0 to 5%, keeps the temperature of described substrate not to be higher than 100 ℃ simultaneously;

Wherein said photopolymerization and hardening composition comprise (A) free yl polymerizating monomer, (B) photochromic compound and (C) Photoepolymerizationinitiater initiater component, the content of described photochromic compound (B) is 0.2 to 20% weight, in per 100 weight portion free yl polymerizating monomers (A), be 0.01 to 10 weight portion as the content of the phosphorous Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater component (C); Simultaneously, described photopolymerization and hardening composition also comprise the Photoepolymerizationinitiater initiater except that phosphorous Photoepolymerizationinitiater initiater as Photoepolymerizationinitiater initiater component (C), and its consumption is per 100 weight portion free yl polymerizating monomers (A), 0.01 to 10 weight portion.

2. the prepared layer tabletting method of claim 1, wherein said photopolymerization and hardening composition can solidify in gas atmosphere.

3. the prepared layer tabletting method of claim 1, wherein said photopolymerization and hardening composition adopt the ultraviolet radiation that contains activation-energy-ray of passing the colour filter that can reduce the wavelength component that is shorter than 300nm.

4. the prepared layer tabletting method of claim 3 wherein uses hard soda-lime glass as described colour filter.

5. the prepared layer tabletting method of claim 3, wherein said photopolymerization and hardening composition adopt and pass described colour filter, pass the ultraviolet radiation that contain activation-energy-ray of heat ray by colour filter then.

6. the prepared layer tabletting method of claim 1, wherein said substrate is the thin substrate that the thickness at described curvature of curved surface center is not more than 2mm.

7. the prepared layer tabletting method of claim 1, wherein use spin-coating method will contain on the photopolymerization of described photochromic compound and phosphorous Photoepolymerizationinitiater initiater and the curved surface that hardening composition is coated onto substrate, and during spin coating, will deposit and remove at the described photopolymerization and the hardening composition of substrate peripheral edge part.

8. photopolymerization and hardening composition, described photopolymerization and hardening composition comprise (A) free yl polymerizating monomer, (B) photochromic compound and (C) Photoepolymerizationinitiater initiater component, the content of described photochromic compound (B) is 0.2 to 20% weight, in per 100 weight portion free yl polymerizating monomers (A), phosphorous Photoepolymerizationinitiater initiater accounts for 0.01 to 10 weight portion and other Photoepolymerizationinitiater initiater except that phosphorous Photoepolymerizationinitiater initiater accounts for 0.01 to 10 weight portion in the Photoepolymerizationinitiater initiater component (C) that is comprised.

9. the laminate of the method preparation by claim 1, described laminate comprises the substrate with curved surface, forming thickness on the curved surface of described substrate is the polymer film of 1 to 100 μ m, described polymer film comprises the photochromic compound of 0.2 to 20% weight, wherein lamination the substrate curved surface before the polymer film the refraction at spherical surface ability and formed difference between the refraction at spherical surface ability of curved surface of polymer film of described laminate less than ± 0.5 diopter, and in the scope of the polymer film of removing form peripheral edge portions, the difference between maximum film thickness or minimum thickness and the average film thickness is not more than 7%.

10. the laminate of claim 9, wherein said substrate are that the glimmer that the thickness at curvature of curved surface center is not more than 2mm is learned element.

11. the laminate of claim 9, wherein said substrate are plastic lens.